KR102289321B1 - Material for light-emitting auxiliary layer comprising ring-fused fluorene compound or fluorene compound - Google Patents

Abstract

(각 식 중, R¹ 및 R²는 치환될 수도 있는 아릴 또는 치환될 수도 있는 페닐 혹은 축합환계 아릴 등이며 그리고, R³ 및 R⁴는 치환될 수도 있는 알킬 또는 치환될 수도 있는 아릴 등이다.)For example, it is an object to provide an organic EL device with improved luminous efficiency by efficiently using the TTF phenomenon. For example, in an organic electroluminescent device, a light-emitting auxiliary layer is provided between the light-emitting layer and the electron-transporting layer, and the light-emitting auxiliary layer is formed by condensing one to three benzene rings on any one of two benzene rings of fluorene. Provided is an organic EL device having improved luminous efficiency by forming a ring-condensed fluorene compound and/or a fluorene compound, for example, a benzofluorene compound or a fluorene compound represented by the following formulas (1) to (3).

(In each formula, R ¹ and R ² are optionally substituted aryl or optionally substituted phenyl or condensed cyclic aryl, and R ³ and R ⁴ are optionally substituted alkyl or optionally substituted aryl. )

Description

A material for a light-emitting auxiliary layer comprising a ring-condensed fluorene compound or a fluorene compound

The present invention relates to a light emission containing a ring-condensed fluorene compound and/or a fluorene compound, particularly a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound and/or a fluorene compound. It relates to a material for an auxiliary layer, an organic electroluminescent device using the same, and a display device.

An organic electroluminescent element (hereinafter also referred to as an "organic EL element") is a light emitting element of a self-emission type, and is expected as a light emitting element for display or illumination. Conventionally, a display device using a light emitting device that emits electroluminescence has been studied in various ways in that it is possible to reduce power consumption and thickness, and furthermore, an organic EL device made of an organic material is easy to reduce in weight or increase in size. has been actively reviewed. In particular, with respect to the development of organic materials having luminescent properties including blue, which is one of the three primary colors of light, and the development of organic materials having charge transport ability (possible to become semiconductors and superconductors) such as holes and electrons, polymers Both compounds and low molecular weight compounds have been actively studied until now.

The organic EL device has a structure comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer or the like disposed between the pair of electrodes and formed of an organic compound. When organic EL devices are classified according to their light emission principle, they can be divided into two types: a fluorescent type and a phosphorescent type. When a voltage is applied to the organic EL device, holes are injected from the anode and electrons are injected from the cathode, and they recombine in the light emitting layer to form excitons. According to the statistical law of electron spin, singlet excitons and triplet excitons are generated at a ratio of 25%:75%. Since the fluorescent type uses light emission by singlet excitons, it has been said that the internal quantum efficiency is 25% as the limit.

However, with respect to a technique for improving the efficiency of a fluorescent device, several techniques for extracting light emission from triplet excitons that have not been effectively utilized so far have been disclosed. For example, in Patent Document 1, in ordinary organic molecules, the lowest triplet excited state (T1) is lower than the lowest singlet excited state (S1), but the high triplet excited state (T2) is higher than S1 in some cases, In this case, it is said that light emission from the singlet excited state can be obtained by the transition from T2 to S1. Further, in Non-Patent Document 1, a non-doped element using an anthracene-based compound as a host material is analyzed, and singlet excitons are generated by collision fusion of two triplet excitons, and as a result, fluorescence is increasing. In particular, the phenomenon in which singlet excitons are generated by collision fusion of these two triplet excitons is called a TTF phenomenon (Triplet-Triplet Fusion).

Further, in Patent Document 2, efficiency improvement of the fluorescent element by efficiently generating this TTF phenomenon is studied. Specifically, when a barrier layer formed of a material having high triplet energy is provided at the interface on the cathode side of the light emitting layer to have a specific relationship between the triplet energy of the host material and the fluorescent dopant material that can be used in the fluorescent device. It is said that triplet excitons are confined in the light emitting layer, and the TTF phenomenon is efficiently caused to realize high efficiency and long life of the fluorescent element.

In Patent Document 2, as a material used for the barrier layer, hydrocarbon aromatic compounds (Claim 4), for example, derivatives such as naphthalene, phenanthrene, chrysene, fluoranthene, triphenylene (paragraphs [0073] to [0094]) ]) are described, and specifically, the EL characteristics of fluoranthene-based compounds and benzochrysene-based compounds ([Formula 34]) have been studied.

In addition, Patent Document 3 describes manufacturing an organic EL device using a benzofluorene-based compound substituted with an aryl group or an amino group, but does not relate to the TTF phenomenon or triplet energy. Only the EL characteristics in the case where a benzofluorene-based compound is used as a material for a light emitting layer have been confirmed.

Further, a dibenzofluorene compound is used as a material for a light-emitting layer (Patent Document 4), an indenotriphenylene compound is used as a material for a light-emitting layer (Patent Document 5, Patent Document 6), or an indenopyrene compound is used as an organic EL compound. Examples used as a material for each layer in an element are known (Patent Document 7, Patent Document 8).

Japanese Patent Laid-Open No. 2004-214180 International Publication No. 2010/134350 Japanese Patent Laid-Open No. 2008-291006 International Publication No. 2011/081403 Chinese Patent Application Publication No. 103508835 International Publication No. 2012/086366 Japanese Patent Laid-Open No. 2011-079822 International Publication No. 2010/053210

Journal of Applied Physics, 102, 114504 (2007)

Under such circumstances, the development of an organic EL device capable of efficiently utilizing the TTF phenomenon, that is, a compound capable of obtaining this device, is required.

As a result of the intensive study of the present inventors in order to solve the above problems, the light emitting auxiliary layer provided between the light emitting layer and the electron transport layer in the organic EL device is formed with a ring-condensed fluorene compound and/or a fluorene compound, particularly a specific benzofluorene compound. By forming an orene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound, and/or a fluorene compound, the TTF phenomenon can be efficiently used, and internal quantum efficiency and external quantum efficiency are improved. It was discovered that an organic EL device was obtained.

[One]

A cyclic condensed fluorene compound in which 1 to 3 benzene rings are condensed on any one of two benzene rings of fluorene as a material for a light emitting auxiliary layer used for a light emitting auxiliary layer between the light emitting layer and the electron transport layer in an organic electroluminescent device And / or a material for a light emitting auxiliary layer comprising a fluorene compound,

The five-membered ring of the condensed ring fluorene compound and the fluorene compound may be substituted with optionally substituted alkyl and/or optionally substituted aryl, and when two substituents are substituted on the five-membered ring, these substituents combine to form a ring can form,

At least a part of the benzene ring and/or the condensed moiety of the ring-condensed fluorene compound may be substituted with optionally substituted aryl, further substituted with optionally substituted alkyl and/or optionally substituted with cycloalkyl, And,

At least a part of the benzene ring of the fluorene compound may be substituted with optionally substituted phenyl or condensed aryl, and may be further substituted with optionally substituted alkyl and/or optionally substituted cycloalkyl, the phenyl or condensed When the substituent for the ring-based aryl is aryl, the aryl is phenyl or condensed ring-type aryl;

A material for a light emitting auxiliary layer.

[2]

The material for the light-emitting auxiliary layer is a material for the light-emitting auxiliary layer including a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound and/or a fluorene compound,

The five-membered ring of the benzofluorene compound, dibenzofluorene compound, indenotriphenylene compound, indenopyrene compound and fluorene compound may be substituted with optionally substituted alkyl and/or optionally substituted aryl, When two substituents are substituted for the five-membered ring, these substituents may combine to form a ring,

At least a part of the benzene ring and/or the condensation site of the benzofluorene compound, the dibenzofluorene compound, the indenotriphenylene compound and the indenopyrene compound is substituted with optionally substituted aryl, and may be further substituted may be substituted with alkyl and/or optionally substituted cycloalkyl, and

At least a part of the benzene ring of the fluorene compound may be substituted with optionally substituted phenyl or condensed aryl, and may be further substituted with optionally substituted alkyl and/or optionally substituted cycloalkyl, the phenyl or condensed When the substituent for the ring-based aryl is aryl, the aryl is phenyl or condensed ring-type aryl;

The material for a light emitting auxiliary layer according to the above [1].

[3]

The fluorene compound is represented by the following general formula (1), the benzofluorene compound is represented by the following general formula (2) or the following general formula (3), and the dibenzofluorene compound is represented by the following general formula (4) ), wherein the indenotriphenylene compound is represented by the following general formula (5) or the following general formula (6), and the indenopyrene compound is represented by the following general formula (7), [2] The material for the light emitting auxiliary layer described in.

[Formula 4]

^{(R 1} and R ² in the formulas (2) to (7) are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and R ¹ and R ^{At least one of 2} is optionally substituted aryl,

^{R 1} and R ² in the formula (1) are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted phenyl or condensed cyclic aryl, and R ¹ and At least one of R ² is optionally substituted phenyl or fused-ring aryl, and when the substituent on the phenyl or fused-ring aryl is aryl, the aryl is phenyl or fused-ring aryl, and

^{R 3} and R ⁴ in the formulas (1) to (7) are each independently optionally substituted alkyl or optionally substituted aryl, and R ³ and R ⁴ may combine to form a ring. .)

[4]

^{R 1} and R ² in the formulas (2) to (7) are each independently hydrogen, optionally substituted alkyl having 1 to 24 carbon atoms, optionally substituted cycloalkyl having 3 to 12 carbon atoms, or substituted optionally aryl having 6 to 30 carbon atoms, ^{and at least one of R 1} and R ² is optionally substituted aryl having 6 to 30 carbon atoms;

^{R 1} and R ² in the formula (1) are each independently hydrogen, optionally substituted alkyl having 1 to 24 carbon atoms, optionally substituted cycloalkyl having 3 to 12 carbon atoms, or optionally substituted C6-C30 phenyl or condensed cyclic aryl, ^{at least one of R 1} and R ² is optionally substituted C6-C30 phenyl or condensed cyclic aryl;

^{R 3} and R ⁴ in the formulas (1) to (7) are each independently an optionally substituted alkyl having 1 to 24 carbon atoms or an optionally substituted aryl having 6 to 30 carbon atoms, R ³ and R ⁴ may combine to form a ring,

^{The substituents in R 1} and R ² in the formulas (2) to (7) are each independently alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 30 carbon atoms,

^{Substituents in R 1} and R ² in Formula (1) are each independently alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, phenyl having 6 to 30 carbon atoms, or condensed cyclic aryl;

^{The substituents in R 3} and R ⁴ in the formulas (1) to (7) are each independently alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 30 carbon atoms,

The material for a light emitting auxiliary layer according to the above [3].

[5]

^{R 1} and R ² in the formulas (2) to (7) are optionally substituted C6-C24 aryl;

^{R 1} and R ² in the formula (1) are optionally substituted C6-C24 phenyl or condensed cyclic aryl;

^{R 3} and R ⁴ in the formulas (1) to (7) are each independently an optionally substituted alkyl having 1 to 12 carbon atoms or an optionally substituted aryl having 6 to 16 carbon atoms, R ³ and R ^{In the} case of tetravalent aryl, aryls may combine to form a ring,

^{Substituents in R 1} and R ² in Formulas (2) to (7) are each independently alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms,

^{Substituents in R 1} and R ² in Formula (1) are each independently alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, phenyl having 6 to 20 carbon atoms, or condensed cyclic aryl,

^{The substituents for R 3} and R ⁴ in the formulas (1) to (7) are each independently alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms,

The material for a light emitting auxiliary layer according to the above [3].

[6]

As a benzofluorene compound represented by the general formula (2) or (3),

R ¹ and R ² are optionally substituted C6-C20 aryl,

R ³ and R ⁴ are each independently an optionally substituted alkyl having 1 to 6 carbon atoms or an optionally substituted aryl having 6 to 12 carbon atoms, and R ³ and when R ⁴ is aryl, aryl may be bonded to each other to form a ring, and

The substituents for R ¹ , R ² , R ³ and R ⁴ are each independently methyl, ethyl, propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl;

The material for a light emitting auxiliary layer according to the above [3].

[7]

As a benzofluorene compound represented by the general formula (2) or (3),

R ¹ and R ² are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl or phenanthryl, and

R ³ and R ⁴ are each independently methyl, ethyl, propyl, t-butyl, phenyl or biphenylyl, phenyl or biphenylyl may be bonded to each other to form a ring,

The material for a light emitting auxiliary layer according to the above [3].

[8]

For the light emitting auxiliary layer according to the above [3], which is represented by any one of the following formulas (2-1), (2-2), (2-3), (2-4) and (2-5) ingredient.

[Formula 5]

[9] Formula (1-1), Formula (1-71), Formula (2-21), Formula (2-41), Formula (2-61), Formula (2-62), Formula (2- 85), Formula (2-87), Formula (3-5), Formula (3-6), Formula (3-8), Formula (5-7) and Formula (6-9) represented by any one of, The material for a light emitting auxiliary layer according to the above [3].

[Formula 6]

[10]

A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport layer disposed between the cathode and the light emitting layer, and a light emitting auxiliary layer disposed between the light emitting layer and the electron transport layer. , as an organic electroluminescent device,

An organic electroluminescent device, wherein the light-emitting auxiliary layer is formed of the light-emitting auxiliary layer material according to any one of [1] to [9].

[11]

The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,

The triplet energy E ^T _h of the host material is smaller than the ^{triplet energy E T} _{a of the} material for the light emitting auxiliary layer,

The organic electroluminescent device according to the above [10].

[12]

The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,

The triplet energy E ^T _d of the dopant material is greater than the ^{triplet energy E T} _h of the host material,

The organic electroluminescent device according to the above [10] or [11].

[13]

The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,

The host material contains at least one selected from the group consisting of anthracene derivatives and pyrene derivatives,

The dopant material contains at least one selected from the group consisting of an amine-containing benzofluorene derivative, an amine-containing pyrene derivative, an amine-free pyrene derivative, an amine-containing chrysene derivative, and an amine-containing styryl derivative.

The organic electroluminescent device according to any one of [10] to [12].

[14]

The organic electroluminescent device according to any one of [10] to [13], wherein the material for the electron transport layer contains a heterocyclic compound.

[15]

The compound according to [14], wherein the heterocyclic compound is at least one selected from the group consisting of pyridine derivatives, thiazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, phenanthroline derivatives and phosphine oxide derivatives. electroluminescent device.

[16]

The Bahia relationship Community A _e of the material for the electron transport layer to form a community Bahia A _a and the electron transport layer of the light-emitting auxiliary material, A _a> A _e of -0.8eV,

The organic electroluminescent device according to any one of [10] to [15].

[17]

A display device provided with the organic electroluminescent device according to any one of [10] to [16].

[18]

A lighting device provided with the organic electroluminescent device according to any one of [10] to [16].

According to a preferred aspect of the present invention, it is possible to provide an organic EL device in which the TTF phenomenon occurring in the light emitting layer can be efficiently used and the external quantum efficiency is improved. Further, by improving the external quantum efficiency, the applied electric charge can be efficiently used, so that it is possible to provide an organic EL device in which deterioration of the organic EL device is suppressed and the device life is further improved.

1 is a schematic cross-sectional view showing an organic EL device according to the present embodiment.

One. organic electric field light emitting device

An organic EL device using a material for a light emitting auxiliary layer according to the present invention will be described in detail with reference to the drawings. 1 is a schematic sectional view showing an organic EL device according to the present embodiment.

<Structure of organic EL device>

The organic EL device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer ( The hole transport layer 104 provided on the 103), the light emitting layer 105 provided on the hole transport layer 104, the light emitting auxiliary layer 110 provided on the light emitting layer 105, and the light emitting auxiliary layer 110 provided on the It has an electron transport layer 106 , an electron injection layer 107 provided on the electron transport layer 106 , and a cathode 108 provided on the electron injection layer 107 .

In addition, the organic EL device 100 is manufactured by reversing the manufacturing order, for example, the substrate 101, the cathode 108 provided on the substrate 101, and the electron injection layer provided on the cathode 108 ( 107), the electron transport layer 106 provided on the electron injection layer 107, the light emitting auxiliary layer 110 provided on the electron transport layer 106, and the light emitting layer 105 provided on the light emission auxiliary layer 110 and , a hole transport layer 104 provided on the light emitting layer 105, a hole injection layer 103 provided on the hole transport layer 104, and an anode 102 provided on the hole injection layer 103 there is.

It is not necessary to have all of the above layers, and the minimum structural unit is made up of the anode 102, the light emitting layer 105, the light emitting auxiliary layer 110, the electron transport layer 106, and the cathode 108, and the hole injection layer (103), the hole transport layer 104, and the electron injection layer 107 is an arbitrarily provided layer. In addition, each of the layers may be formed of a single layer or a plurality of layers, respectively.

As an aspect of the layer constituting the organic EL element, in addition to the configuration aspect of "substrate / anode / hole injection layer / hole transport layer / light emitting layer / light emitting auxiliary layer / electron transport layer / electron injection layer / cathode" described above, "substrate / Anode / hole transport layer / light emitting layer / light emitting auxiliary layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / light emitting auxiliary layer / electron transport layer / electron injection layer / cathode", "substrate / anode" /Hole injection layer / hole transport layer / light emitting layer / light emitting auxiliary layer / electron transport layer / cathode", "substrate / anode / light emitting layer / light emitting auxiliary layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer /Emission auxiliary layer/electron transport layer/cathode”, “substrate/anode/hole injection layer/light-emitting layer/light-emission auxiliary layer/electron transport layer/cathode” and “substrate/anode/light-emitting layer/light-emission auxiliary layer/electron transport layer/cathode” It could be the sun.

2. light emitting layer

The role of the light emitting auxiliary layer is to first suppress or prevent diffusion of triplet excitons generated in the light emitting layer into the electron transport layer (contain triplet excitons in the light emitting layer), thereby efficiently generating the TTF phenomenon in the light emitting layer. In addition, the next role of the light-emitting auxiliary layer is to efficiently inject electrons from the cathode into the light-emitting layer. Although this role is originally played by the electron transport layer (and electron injection layer), since the light emission auxiliary layer is disposed between the light emitting layer and the electron transport layer, the electron injection property from the electron transport layer to the light emitting layer is greatly reduced or not inhibited. It is preferable not to

<Material for light-emitting auxiliary layer>

The material for the light emitting auxiliary layer according to the present invention is a ring-condensed fluorene compound (a compound in which 1 to 3 benzene rings are condensed to any one of the two benzene rings of fluorene) and/or a fluorene compound, in particular, a specific benzofluorene compound. an orene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound, and/or a fluorene compound;

The ring-condensed fluorene compound and/or fluorene compound, in particular, a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound and a fluorene compound,

The five-membered ring may be substituted with optionally substituted alkyl and/or optionally substituted aryl, and when two substituents are substituted on the five-membered ring, these substituents may combine to form a ring,

At least a part of the benzene ring (the side in which the benzene rings of the two benzene rings of the fluorene are not condensed) and/or the condensed portion of the ring-condensed fluorene compound is substituted with optionally substituted aryl, which may be further substituted may be substituted with alkyl and/or optionally substituted cycloalkyl, and

At least a part of the benzene ring (either or both of the two benzene rings of fluorene) of the fluorene compound is substituted with optionally substituted phenyl or condensed aryl, optionally substituted with alkyl and/or substituted It may be substituted with a cycloalkyl which may

A ring-condensed fluorene compound is the compound which 1-3 benzene rings condensed to either of the two benzene rings of fluorene. In addition, although the number of the benzene rings condensed to either one of the two benzene rings of fluorene may be 1-3, Preferably it is 1 or 2, More preferably, it is 1 piece. "Condensing" includes not only the form directly condensed with fluorene skeleton as illustrated below as an example, but also the form of further condensing with the benzene ring directly condensed with fluorene. The "condensation site" means a grouping portion of a ring containing a benzene ring derived from fluorene, which is formed by condensation on a fluorene skeleton as illustrated by way of example below. Among the ring-condensed fluorene compounds, a compound in which one benzene ring is condensed on one benzene ring in fluorene, that is, a benzofluorene compound is the most preferable.

[Formula 7]

The cyclic condensed fluorene compound and fluorene compound that can be used as the material for the light-emitting auxiliary layer, in particular, a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound, and a fluorene compound are described above. As described above, the five-membered ring in the structure, the benzene ring belonging to the fluorene skeleton, and the condensation site formed by the condensation of the benzene ring on the fluorene skeleton may be substituted with various substituents, but these substituents are described later in the general formula (1) to What was demonstrated in (3) and Formula (4) - (7) can be cited. In addition, the number of substituents on the benzene ring and the condensation site, the combination of substituents, or the substitution position does not prevent the diffusion of triplet excitons into the electron transport layer at all, or increases the electron injection property from the electron transport layer to the light emitting layer. It does not specifically limit, unless there is a thing inhibiting.

As the benzofluorene compound and the fluorene compound that can be used as the material for the light-emitting auxiliary layer, those represented by the following general formulas (1) to (3) are particularly preferable.

[Formula 8]

As the dibenzofluorene compound, indenotriphenylene compound and indenopyrene compound that can be used as the material for the light emitting auxiliary layer, those represented by the following general formulas (4) to (7) are particularly preferable.

[Formula 9]

In the general formula (1),

R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted phenyl or condensed aryl, and at least one of ^{R 1} and R ^{2 is substituted} phenyl or condensed cyclic aryl which may be, and

R ³ and R ⁴ are each independently optionally substituted alkyl or optionally substituted aryl, and R ³ and R ⁴ may be combined to form a ring.

In the general formulas (2) to (7),

R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, ^{at least one of R 1} and R ² is optionally substituted aryl, And,

R ³ and R ⁴ are each independently optionally substituted alkyl or optionally substituted aryl, and R ³ and R ⁴ may be combined to form a ring.

As "phenyl or condensed cyclic aryl" of "optionally substituted phenyl or condensed cyclic aryl" ^{in R 1} and R ² in formula (1), for example, phenyl or condensed aryl having 6 to 30 carbon atoms can be heard The "phenyl or condensed cyclic aryl" of R ¹ and R ² is preferably a phenyl or condensed ring aryl having 6 to 24 carbon atoms, more preferably a phenyl or condensed ring aryl having 6 to 20 carbon atoms, still more preferably 6 carbon atoms. ~12 phenyl or condensed cyclic aryl.

As "aryl" of "aryl which may be substituted" in ^R<1> and R<^2> of General formula (2)-(7), C6-C30 aryl is mentioned, for example. As "aryl" of R<^1> and R<^2> , Preferably it is C6-C24 aryl, More preferably, it is C6-C20 aryl, More preferably, it is C6-C12 aryl.

Examples of the "aryl" of the "optionally substituted aryl" ^{in R 3} and R ⁴ in formulas (1) to (7) include aryl having 6 to 30 carbon atoms. The "aryl" of R ³ and R ⁴ is preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms.

^{Specific examples of “fused-ring aryl” for R 1} and R ² in Formula (1) include (1-,2-)naphthyl, which is fused-bicyclic aryl, and acenaphthylene-(1-,3-) which is fused-tricyclic aryl. ,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenanthrene-(1-,2-)yl, (1-,2-,3 -,4-,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2 -,5-)yl, perylene-(1-,2-,3-)yl which is a condensed pentacyclic aryl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

^{Specific "aryl" for R 1} and R ² in formulas (2) to (7) includes phenyl which is monocyclic aryl, (2-,3-,4-)biphenylyl which is bicyclic aryl, and condensed bicyclic aryl. (1-,2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-ter Phenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl- 4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p -terphenyl-4-yl), condensed tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9 -)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m- Terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenyl), condensed tetracyclic aryl triphenylene- (1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2-,5-)yl, perylene-(1-,2 condensed pentacyclic aryl) -,3-)yl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

^{Specific "aryl" for R 3} and R ⁴ in formulas (1) to (7) includes phenyl which is monocyclic aryl, (2-,3-,4-)biphenylyl which is bicyclic aryl, and condensed bicyclic aryl. (1-,2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-ter Phenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl- 4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p -terphenyl-4-yl), condensed tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9 -)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m- Terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenyl), condensed tetracyclic aryl triphenylene- (1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2-,5-)yl, perylene-(1-,2 condensed pentacyclic aryl) -,3-)yl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

^{Particularly preferred "phenyl or condensed-cyclic aryl" in R 1} and R ² in the general formula (1) are phenyl, naphthyl and phenanthryl, and among these, phenyl, 1-naphthyl, 2-naphthyl and 9-phenanthryl is preferred. Further, R ¹ and R ² may be the same or different, preferably R ¹ and R ² are the same.

^{Particularly preferred "aryl" in R 1} and R ² in formulas (2) to (7) is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl and phenanthryl, among these, Phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl and 9-phenanthryl are preferred. Further, R ¹ and R ² may be the same or different, preferably R ¹ and R ² are the same.

In addition, in the R ¹ and R ² in the formula (1) "a condensed polycyclic aryl group" or the formula (2) to "aryl" in R ¹ and R ² of (7), the general formula (1) It may be a compound of to (7) (with the proviso that R ¹ and R ² are excluded), and in this case, it is a compound in which any two of the compounds of general formulas (1) to (7) are directly bonded.

Particularly preferred "aryl" in R ³ and R ⁴ is phenyl, 4-biphenylyl, 1-naphthyl and 2-naphthyl, R ³ and R ⁴ may be the same or different, preferably Preferably R ³ and R ⁴ are the same.

As "alkyl" of "which may be substituted alkyl" in ^{R 1} , R ² , R ³ and R ⁴ in formulas (1) to (3) and formulas (4) to (7), straight-chain and branched Any one of the chains may be sufficient, for example, C1-C24 linear alkyl or C3-C24 branched chain alkyl is mentioned. Preferred "alkyl" is C1-C18 alkyl (C3-C18 branched chain alkyl). A more preferable "alkyl" is C1-C12 alkyl (C3-C12 branched alkyl). A more preferable "alkyl" is C1-C6 alkyl (C3-C6 branched alkyl). A particularly preferable "alkyl" is C1-C4 alkyl (C3-C4 branched alkyl).

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

As "cycloalkyl" of "cycloalkyl which may be substituted" in ^{R 1} and R ² in formulas (1) to (3) and general formulas (4) to (7), for example, C3-C3 and cycloalkyl of 12. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

^{Examples of the "substituent" in R 1} and R ² in the general formula (1) include alkyl, cycloalkyl, phenyl, or condensed cyclic aryl, and preferred ones thereof are those described in the "alkyl" column above. those described in the column of "cycloalkyl", and those described in the column of "phenyl or condensed cyclic aryl" in ^{R 1} and R ^{2 in the general formula (1).}

^{Examples of the "substituent" in R 1} and R ² in the general formulas (2) to (7) include alkyl, cycloalkyl, and aryl. Preferred examples of these are those described in the "alkyl" column above. , those described in the column of "cycloalkyl", and the same ones as those described in the column of "aryl" above.

^{Examples of the "substituent" for R 3} and R ⁴ in the general formulas (1) to (7) include alkyl, cycloalkyl, and aryl. Preferred examples of these are those described in the "alkyl" column above. , those described in the column of "cycloalkyl", and the same ones as those described in the column of "aryl" above.

In addition, ^{the "substituent" in R 1} and R ² in the general formulas (1) to (7) may be a compound of the general formulas (1) to (7) (with the proviso that the structural moiety excluding ^{R 1} and R ^{2 ) may be} In this case, any two of the compounds of the general formulas (1) to (7) become a compound in which “aryl” or “phenyl or condensed cyclic aryl” is interposed.

As ^{the “substituent” for R 1} , R ² , R ³ and R ⁴ , specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n -pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tri alkyl such as decyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; Phenyl, biphenylyl ( ^{excluding substituents for R 1} and R ^{2 in} Formula (1)), naphthyl, terphenylyl (excluding substituents for ^{R 1} and R ^{2 in Formula (1))} , aryl such as phenanthryl; Methylphenyl, ethylphenyl, s-butylphenyl, t-butylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1,6-dimethylnaphthyl, 2,6-dimethylnaphthyl, 4-t-butylnaphthyl Alkylaryl, such as these, etc. are mentioned. The number of substituents is, for example, a maximum substitutable number, preferably 0 to 3, more preferably 0 to 2, still more preferably 0 (unsubstituted).

At least one of R ¹ and R ² is selected from optionally substituted aryl or optionally substituted phenyl or condensed cyclic aryl, preferably both of R ¹ and R ² are optionally substituted aryl or optionally substituted. phenyl or condensed cyclic aryl, and in this case, it is more preferable that the same group is selected for both ^{R 1} and R ^{2 .}

R ³ and R ⁴ may combine to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or Indene and the like may be spiro-coupled.

In addition, a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, an indenotriphenylene ring, or All or part of the hydrogen atoms in the indenopyrene ring and the hydrogen atoms in the substituents R ¹ to R ^{4 may be deuterium.}

<Triplet energy of material for light-emitting auxiliary layer>

The role of the light emitting auxiliary layer is to suppress or prevent diffusion of triplet excitons generated in the light emitting layer into the electron transport layer (contain triplet excitons in the light emitting layer), thereby efficiently generating the TTF phenomenon in the light emitting layer. Although the present invention is not limited to a specific principle, in order to achieve this role, for example, the triplet energy E ^T _a of the material for the light emitting auxiliary layer is preferably larger than the ^{triplet energy E T} _h of the host material of the light emitting layer. Further, the relationship between, the triplet energy of the host material and a dopant material which forms the light-emitting layer as described later is E ^T _h <E it is preferable to satisfy a relation of ^T _d, the light-emitting triplet energy of the secondary layer material E ^T _a It is more preferable that the ^{triplet energy E T} _d of the dopant material of the provisional light emitting layer is larger than that of the dopant material. In this way, singlet excitons can be efficiently generated from triplet excitons of the host in the light emitting layer, and energy deactivation can be optically performed by moving the singlet excitons onto the fluorescent dopant.

In addition, in the present specification, triplet energy means the difference between the energy in the lowest excited triplet state and the energy in the ground state, and the singlet energy (sometimes referred to as an energy gap) is the lowest excitation singlet. It is the difference between the energy in the state and the energy in the ground state.

A ring-condensed fluorene compound and/or a fluorene compound, in particular, a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound, and a fluorene compound as a material for a light emitting auxiliary layer according to the present invention , since it has a relatively high triplet energy E ^T _a derived from the specific structure described above, for most materials generally used as host materials and fluorescent dopant materials for organic EL devices, 3 generated in the light emitting layer Diffusion of singlet excitons into the electron transport layer can be suppressed or prevented. As a result, the TTF phenomenon can be efficiently generated in the light emitting layer. Moreover, this effect can be heightened especially by combining with the specific host material and fluorescent dopant material mentioned later.

<Affinity of material for light-emitting auxiliary layer>

The next role of the light-emitting auxiliary layer is to efficiently inject electrons from the cathode into the light-emitting layer. Although this role is originally played by the electron transport layer (and electron injection layer), since the light emission auxiliary layer is disposed between the light emitting layer and the electron transport layer, the electron injection property from the electron transport layer to the light emitting layer is greatly reduced or not inhibited. It is preferable not to When the electron injection property into the light emitting layer is greatly reduced or the electron-hole recombination in the light emitting layer is reduced, the density of triplet excitons is reduced, and the collision frequency of triplet excitons is reduced. As a result, the TTF phenomenon does not occur efficiently. do. Although the present invention is not limited to a specific principle, in order to achieve this role, for example, the relation between the affinity _{A a of the material for the light emitting auxiliary layer and the affinity A e} of the material for the electron transport layer _{is, A a} >A _e - It is preferable to satisfy 0.8 eV. This relationship, A _a> It is more preferred that it is more preferable to satisfy A _e -0.6eV, and satisfies _{A a>} A _e -0.5eV. If the electron injection from the electron transport layer to the light emitting auxiliary layer is greatly damaged, electrons are accumulated in the electron transport layer, resulting in a high voltage, and there is a possibility that the stored electrons collide with triplet excitons and energy is changed.

A ring-condensed fluorene compound and/or a fluorene compound, in particular, a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, an indenopyrene compound, and a fluorene compound as a material for a light emitting auxiliary layer according to the present invention _{, has a relatively large affinity A a} derived from the above-described specific structure, so that, for most materials generally used as electron transport materials for organic EL devices, the electron injection property from the electron transport layer to the light emitting layer is greatly reduced. There is nothing to do or hinder. Moreover, this effect can be heightened especially by combining with the material for specific electron-transporting layers mentioned later.

<Specific compound of material for light emitting auxiliary layer>

Specific examples of the material for the light-emitting auxiliary layer include all compounds obtained from a combination of the ^{central skeleton shown below, a substituent R 1} or R ² , and a substituent R ³ or R ^{4 .} However, the following formulas (5) to (12) are not selected as ^{substituents R 1} or R ² of the central skeleton (fluorene skeleton) of the formula (1).

[Formula 10]

[Formula 11]

[Formula 12]

That is, as a specific compound of the material for the light emitting auxiliary layer, in the central skeleton selected from any one of Formulas (1) to (3) and Formulas (4) to (7), Formulas (1) to (8) and Formulas A substituent selected from any one of (13) to (19) ^{is bonded to R 1} or R ² (R ¹ and R ² may be different or the same), and from any one of Formulas (1) to (10) and a compound to which the selected substituent R ³ or R ⁴ (R ³ and R ⁴ may be different or the same) is bonded. However, the following formulas (5) to (12) are not selected as ^{substituents R 1} or R ² of the central skeleton (fluorene skeleton) of the formula (1). In the above formula, ^{formula (5) of a preferable example of the substituent R 3} or R ⁴ represents a form in which a 5-membered ring in the structure of Formula (5) is spiro bonded to a 5-membered ring of the central skeleton, "Me" is methyl, "Et"" means ethyl, "tBu" means t-butyl, "Hexyl" means hexyl, and "Octyl" means octyl.

In particular, as the fluorene compound of the general formula (1), a compound represented by any one of the following formulas is preferable.

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

In particular, as the benzofluorene compound of the general formula (2), a compound represented by any one of the following formulas is preferable.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

In particular, as the benzofluorene compound of the general formula (3), a compound represented by any one of the following formulas is preferable.

[Formula 24]

In particular, as the dibenzofluorene compound of the general formula (4), a compound represented by any one of the following formulas is preferable.

[Formula 25]

In particular, as the indenotriphenylene compound of the general formula (5), a compound represented by any one of the following formulas is preferable.

[Formula 26]

In particular, as the indenotriphenylene compound of the general formula (6), a compound represented by any one of the following formulas is preferable.

[Formula 27]

In particular, as the indenopyrene compound of the general formula (7), a compound represented by any one of the following formulas is preferable.

[Formula 28]

More preferable compounds are the following compounds.

Formula (1-1), Formula (1-3), Formula (1-5), Formula (1-7) - Formula (1-9), Formula (1-11);

Formula (1-21), Formula (1-23), Formula (1-25), Formula (1-27) - Formula (1-29), Formula (1-31);

Formula (1-41), Formula (1-43), Formula (1-45), Formula (1-47) - Formula (1-49), Formula (1-51);

Formula (1-63), Formula (1-67), Formula (1-73), Formula (1-77), Formula (1-81), Formula (1-83) Formula (1-87);

Formula (2-1), Formula (2-3), Formula (2-5), Formula (2-7) - Formula (2-9), Formula (2-11);

Formula (2-21), Formula (2-23), Formula (2-25), Formula (2-27) - Formula (2-29), Formula (2-31);

Formula (2-41), Formula (2-43), Formula (2-45), Formula (2-47) - Formula (2-49), Formula (2-51);

Formulas (2-62) to (2-68);

Formula (2-72) to Formula (2-78);

Formulas (2-82) to (2-88);

Formula (2-91), Formula (2-93), Formula (2-97), Formula (2-101), Formula (2-103), Formula (2-107), Formula (2-111), Formula (2-113), formula (2-117);

Formula (3-1), Formula (3-3), Formula (3-5), Formula (3-7) - Formula (3-9), Formula (3-11);

Formula (4-1), Formula (4-3), Formula (4-5), Formula (4-7) - Formula (4-9), Formula (4-11);

Formula (5-41), Formula (5-43), Formula (5-45), Formula (5-47) - Formula (5-49), Formula (5-51);

Formula (6-1), Formula (6-3), Formula (6-5), Formula (6-7) - Formula (6-9), Formula (6-11);

Formula (7-1), Formula (7-3), Formula (7-5), Formula (7-7) - Formula (7-9), and Formula (7-11).

<Method of manufacturing material for light-emitting auxiliary layer>

The benzofluorene compound represented by the general formula (2) can be produced, for example, by using a known synthesis method such as a Suzuki coupling reaction. The Suzuki coupling reaction is a method of coupling an aromatic halide or triflate and an aromatic boronic acid or an aromatic boronic acid ester in the presence of a base using a paradium catalyst. Specific examples of the reaction route for obtaining the general formula (2) in this way are as follows (Schemes 1 to 3). Each of the schemes of the R ¹ ~ R ⁴ are the same as above, TfO is triflate.

[Formula 29]

Specific examples of the palladium catalyst used in this reaction are Pd(PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd(OAc) ₂ , tris(dibenzylideneacetone)ipalladium(0), tris(di Benzylideneacetone)ipalladium(0)chloroform complex, bis(dibenzylideneacetone)paldium(0), and the like. In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri(t-butyl)phosphine, tricyclohexylphosphine, 1-(N,N-dimethylaminomethyl)-2-(dit-butylphosphino)ferrocene, 1- (N,N-dibutylaminomethyl)-2-(dit-butylphosphino)ferrocene, 1-(methoxymethyl)-2-(dit-butylphosphino)ferrocene, 1,1'-bis( Dit-butylphosphino)ferrocene, 2,2'-bis(dit-butylphosphino)-1,1'-binaphthyl, 2-methoxy-2'-(dit-butylphosphino)- 1,1'-binaphthyl and the like.

Specific examples of the base used in this reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, tripotassium phosphate, potassium fluoride, etc.

Specific examples of the solvent used in this reaction include benzene, toluene, xylene, N,N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butylmethyl ether, 1,4-dioxane, methanol , ethanol, isopropyl alcohol, and the like. These solvents can be appropriately selected according to the structures of the aromatic halide, triflate, aromatic boronic acid ester and aromatic boronic acid to be reacted. A solvent may be used independently and may be used as a mixed solvent.

^{In addition, about the compound which R<3>} and R<^4> couple|bonded to form the ring (for example, an aliphatic ring or an aromatic ring) in the benzofluorene compound represented by General formula (2), for example, Unexamined-Japanese-Patent No. 2009- It can be prepared with reference to the method for producing a benzofluorene compound having a spiro structure described in Publication No. 184993. Paragraph [0055] of the publication describes a method for preparing a compound in which a fluorene ring is spiro-bonded with a five-membered ring of a benzofluorene ring (Scheme 1c). The benzofluorene compound shown can be prepared. In addition, M in the following scheme is Li, MgCl, MgBr, or MgI.

[Formula 30]

Although the above is the manufacturing method of the benzofluorene compound represented by General formula (2), It manufactures by the same method also about the benzofluorene compound represented by General formula (3) and the fluorene compound represented by General formula (1). can do. Further, the compounds of the present invention include those in which at least a part of hydrogen atoms are substituted with deuterium, and such compounds can be produced in the same manner as described above by using a raw material in which the desired sites are deuterated.

In addition, also about the dibenzofluorene compound represented by General formula (4), by making a raw material into a dibenzofluorene compound instead of a benzofluorene compound, it refers to the said scheme (1)-(4), and manufactures it similarly. can do. In addition, the manufacturing method described in the said patent document 4 (International Publication No. 2011/081403) can also be referred to.

Also, for the indenotriphenylene compound represented by the general formula (5) or (6), the above schemes (1) to (4) can be obtained by using an indenotriphenylene compound instead of the benzofluorene compound as the raw material. For reference, it can be prepared similarly. In addition, the manufacturing method described in the said patent document 5 (Chinese Patent Application Publication No. 103508835) or document 6 (International Publication No. 2012/086366) can also be referred to.

In addition, also for the indenopyrene compound represented by the general formula (7), by using the indenopyrene compound as the raw material instead of the benzofluorene compound, it can be prepared in the same manner with reference to the above schemes (1) to (4). there is. Moreover, the manufacturing method described in the said patent document 7 (Unexamined-Japanese-Patent No. 2011-079822) or document 8 (International Publication No. 2010/053210) can also be referred to.

<Other materials for light-emitting auxiliary layer>

Other materials for the light emitting auxiliary layer include, for example, naphthalene derivatives, phenanthrene derivatives, benzophenanthrene derivatives, dibenzophenanes described in paragraphs [0079] to [0093] of Patent Document 2 (International Publication No. 2010/134350). and a trene derivative, a chrysene derivative, a benzochrysene derivative, a fluoranthene derivative, and a triphenylene derivative, and may be used in combination with a benzofluorene compound and a fluorene compound as a material for a light emitting auxiliary layer according to the present invention.

3. Organic EL device substrate

The substrate 101 serves as a support for the organic EL device 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, or a plastic sheet is used. Among them, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate or polysulfone are preferable. If it is a glass substrate, soda-lime glass, alkali-free glass, etc. are used, and since thickness sufficient to maintain mechanical strength is sufficient, for example, it may be 0.2 mm or more. As an upper limit of thickness, it is 2 mm or less, for example, Preferably it is 1 mm or less. For the material of the glass, so it is good with less ion elution from the glass side one side of an alkali-free glass preferably, SiO ₂ subjected to the barrier coat, such as soda lime glass on the market also can use it. In addition, in order to enhance the gas barrier properties, a gas barrier film such as a dense silicon oxide film may be provided on at least one side of the substrate 101, and a synthetic resin plate, film or sheet having a low gas barrier property is applied to the substrate 101. It is preferable to provide a gas barrier film when using it as

4. Organic EL element's anode

The anode 102 serves to inject holes into the light emitting layer 105 . In addition, 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 for forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), etc.), metal halide ( copper iodide, etc.), copper sulfide, carbon black, ITO glass, nesa glass, etc. are mentioned. 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 used by selecting suitably from the materials used as an anode of an organic electroluminescent element.

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

5. Organic EL minor hole injection layer and hole transport layer

The hole injection layer 103 serves to efficiently inject holes moved from the anode 102 into the light emitting layer 105 or the hole transport layer 104 . The hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105 . Each of the hole injection layer 103 and the hole transport layer 104 is formed by laminating and mixing one or two or more of the hole injection and transport materials, or a mixture of the hole injection and transport material and the polymer binder. In addition, the layer may be formed by adding an inorganic salt such as iron (III) chloride to the hole injection/transport material.

As the hole injection/transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is given, and it is desirable to have high hole injection efficiency and to efficiently transport the injected holes. For this purpose, it is preferable that the ionization potential is small, the hole mobility is large, and furthermore, the material is excellent in stability, and the impurity that becomes a trap is not easily generated during manufacture and use.

Materials for forming the hole injection layer 103 and the hole transport layer 104 include a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, a hole injection layer of an organic EL device, and Any one of the known ones used for the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), and triarylamine Derivatives (polymers having aromatic tertiary amino in the main chain 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 (hereinafter abbreviated as NPD), N ,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl Triphenylamine derivatives such as -4,4'-diphenyl-1,1'-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburstamine derivatives, etc.; Stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazine-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, heterocyclic compounds such as porphyrin derivatives, polysilane, etc. Polymers In the system, polycarbonate, styrene derivatives, polyvinyl carbazole, and polysilane having the above monomer in the side chain are preferable, but it is possible to form a thin film necessary for manufacturing a light emitting device, inject holes from the anode, and further transport holes It will not specifically limit if it is a compound which can do it.

It is also known that the conductivity of an organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a good electron accepting compound. For doping of the electron donor material, a strong electron acceptor such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) is used. known (eg, M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998) and J. Blochwitz). , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731 (1998)). These generate so-called holes by the electron transfer process in the electron-donating type base material (hole-transporting material). Depending on the number and mobility of holes, the conductivity of the base material changes significantly. As a matrix material having hole transport properties, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine ZnPc, etc.) are known (Japanese Patent Laid-Open 2005) -167175 publication).

6. Organic EL minor light emitting layer

The light emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light emitting compound), and can form a stable thin film, and is solid and exhibits strong fluorescence efficiency. It is preferable that it is a compound.

The light emitting layer may consist of a single layer or a plurality of layers, or may be any, and each is formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material, or a host material alone, or any there is. That is, in each layer of the light emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. Each of the host material and the dopant material may be one type, or a combination of a plurality of them may be used. The dopant material may be contained in the whole host material, or may be contained partially, either may be sufficient as it. The amount of the dopant used varies depending on the dopant, and may be determined according to the characteristics of the dopant. The standard of the usage-amount of a dopant becomes like this. Preferably it is 0.001 to 50 weight% of the whole light emitting material, More preferably, it is 0.1 to 10 weight%, More preferably, it is 1 to 5 weight%. As a doping method, it can be formed by the co-evaporation method with a host material, but it can also vapor-deposit simultaneously after mixing with a host material beforehand.

In particular, it is preferable to form a light emitting layer from the dopant material of the fluorescent emission property and a host material, the light emission wavelength of which has a peak in 400 ~ 500nm (peak wavelength, concentration: 10 ^-5 to ^10-6 as measured in toluene solution in mol / l In one emission spectrum, it refers to the peak wavelength of the emission spectrum at which the emission intensity is maximum). Holes injected from the anode pass through the hole injection/transport layer and are injected into the emission layer, and electrons injected from the cathode pass through the electron injection/transport layer and the emission auxiliary layer and are injected into the emission layer. Thereafter, holes and electrons recombine in the light emitting layer, and singlet excitons and triplet excitons are generated.

In this case, there are two types of recombination occurring on the host molecule and the case on the dopant molecule. Here, the triplet energy E ^T _d of the dopant material is preferably larger than the ^{triplet energy E T} _h of the host material. With this energy relationship (E ^T _h < E ^T _d ), triplet excitons generated after recombination on the host do not migrate to a dopant having a higher triplet energy, and triplet excitons generated by recombination on the dopant molecule energy transfers rapidly to the host molecule. That is, the density of triplet excitons on the host can be increased, and singlet excitons can be efficiently generated by efficiently colliding triplet excitons on the host with each other (efficient TTF phenomenon). In addition, since the singlet energy E ^S _d of the dopant is smaller than the singlet energy E ^S _h of the host, the singlet excitons generated by the TTF phenomenon transfer energy from the host to the dopant and contribute to fluorescence emission of the dopant. Originally, in the dopant used for a fluorescent device, the transition from the triplet excited state to the ground state is forbidden, and in this transition, the triplet excitons do not cause optical energy deactivation but are thermally deactivated. However, by making the relationship between the triplet energy of the host and the dopant as described above, singlet excitons can be efficiently generated by collision with each other before the triplet excitons cause thermal deactivation, and the luminous efficiency can be improved.

In addition, as for the selection of the host material and the dopant material in consideration of the triplet energy of the light-emitting auxiliary layer, the benzofluorene compound and the fluorene compound as the material for the light-emitting auxiliary layer of the present invention have relatively high triplet energy E ^T because of the _a, it can, usually is used to select a material which, confined the triplet excitons generated in the light emitting layer into the light-emitting layer occurs efficiently TTF developing an organic EL device host material and a fluorescent luminescent dopant materials.

In addition, in order to efficiently generate the TTF phenomenon, the present invention is not limited to a specific principle, but for the host material, the triplet energy E ^T _h is smaller than the ^{triplet energy E T} _a of the light emitting auxiliary layer material. desirable. Also, it is preferable to select a dopant material whose triplet energy E ^T _d ^{is smaller than the triplet energy E T} _a of the light emitting auxiliary layer material.

<Host Material>

Examples of the host material include anthracene derivatives and pyrene derivatives.

<Anthracene derivative as host material>

Anthracene derivatives are, for example, those represented by the following formula (H1).

[Formula 31]

In the formula (H1),

R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 12 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably having 6 to 30 carbon atoms). of aryl),

Ar ¹¹ and Ar ¹² are each independently an optionally substituted aryl (preferably an optionally substituted C6-C30 aryl);

n is an integer of 1 to 3, and when n is 2 or more, each anthracene structure shown in square brackets may be the same or different, and

At least one hydrogen in the anthracene derivative may be substituted with deuterium.

Ar ¹¹ and Ar ¹² each independently represent optionally substituted aryl (preferably, optionally substituted aryl having 6 to 30 carbon atoms), and Ar ¹¹ and Ar ¹² may be different or the same. Preferred aryl is C6-C18 aryl, More preferably, it is C6-C14 aryl, More preferably, it is C6-C12 aryl.

Specific examples of “aryl having 6 to 30 carbon atoms” include phenyl which is a monocyclic aryl, (1-,2-)naphthyl which is a condensed bicyclic aryl, acenaphthylene-(1-,3-,4-, 5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4- ,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2-,5- )yl, perylene-(1-,2-,3-)yl which is condensed pentacyclic aryl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

Preferred "C6-C30 aryl" includes phenyl, naphthyl, phenanthryl, glycenyl or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl. , and particularly preferably phenyl, 1-naphthyl or 2-naphthyl.

The substituent to "aryl having 6 to 30 carbons" is not particularly limited as long as the desired properties are obtained, but preferably, alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons, aryl having 6 to 18 carbons, etc. can be heard

Any of linear and branched chain may be sufficient as "C1-C12 alkyl" as this substituent. That is, straight-chain alkyl having 1 to 12 carbon atoms or branched chain alkyl having 3 to 12 carbon atoms. More preferably, it is C1-C6 alkyl (C3-C6 branched alkyl), More preferably, it is C1-C4 alkyl (C3-C4 branched alkyl). 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, 4-methyl-2-pentyl, 3,3-dimethylbutyl or 2-ethylbutyl, etc. are mentioned, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl is preferred, more preferably methyl, isopropyl or t-butyl.

In addition, as for "C3-C12 cycloalkyl" as this substituent, as a specific example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclo Hexyl etc. are mentioned. Among these, cyclopentyl or cyclohexyl is preferable.

Moreover, about "C6-C18 aryl" as this substituent, C6-C14 aryl is preferable and C6-C10 aryl is especially preferable. Specific examples include phenyl, (2-,3-,4-)biphenylyl, (1-,2-)naphthyl, (1-,2-,3-,4-,9-)phenanthryl, (1-,2-) triphenylenyl and the like.

Ar ¹¹ and Ar ¹² (aryl having 6 to 30 carbon atoms) preferably do not have "substituents", but when they have a substituent, the number of substituents is, for example, the maximum number of substituents, preferably 1 to 3 Dogs, more preferably 1 or 2, still more preferably 1.

R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 12 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably having 6 to 30 carbon atoms). of aryl).

R ¹¹ to R ¹⁸ are “alkyl having 1 to 12 carbons”, “cycloalkyl having 3 to 12 carbons” and “aryl having 6 to 30 carbons”, the specific description of which is described in the Ar ¹¹ and Ar ¹² columns above. can be cited.

n is an integer from 1 to 3. When n is 2 or more, each anthracene structure shown in square brackets may be the same or different. Preferred n is 1 or 2, and more preferred n is 1.

The anthracene derivative represented by the formula (H1) can be prepared using a known raw material and a known synthesis method (see, for example, Japanese Patent Application Laid-Open No. 2012-104806).

Moreover, those represented by the following formula (H2) are preferable as anthracene derivatives.

[Formula 32]

In the formula (H2),

R ¹¹ ~ R ^18, Ar ¹¹ and n, it is possible to cite R ¹¹ ~ R ^18, description of Ar ¹¹ and n in the formula (H1),

A is each independently hydrogen, alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, phenyl or naphthyl, m is an integer of 1 to 5, and,

At least one hydrogen in the anthracene derivative may be substituted with deuterium.

In addition, about C1-C4 alkyl and C3-C6 cycloalkyl, the explanation in Formula (H1) can be quoted.

The anthracene derivative represented by the formula (H2) can be prepared using a known raw material and a known synthesis method (see, for example, Japanese Patent Application Laid-Open No. 2012-104806).

Specific examples of the anthracene derivatives represented by the formulas (H1) and (H2) include those shown below.

[Formula 33]

[Formula 34]

<Pyrene derivative as host material>

The pyrene derivative is, for example, represented by the following formula (H3).

[Formula 35]

In the formula (H3),

^{R 11 ~ R 18, Ar 11} , Ar 12 and n, it is possible to cite ^{R 11 ~ R 18, Ar 11} , Ar ^12, and the description of n in the formula (H1), and,

At least one hydrogen in the pyrene derivative may be substituted with deuterium.

The pyrene derivative represented by the formula (H3) can be prepared using a known raw material and a known synthesis method.

In addition, as a pyrene derivative, one represented by the following formula (H4) is preferable.

[Formula 36]

In the formula (H4),

Any one of R ¹¹ to R ¹⁸ , Ar ¹¹ and Ar ¹² is a bonding group with φ, ^{and the description of R 11} to R ¹⁸ , Ar ¹¹ and Ar ¹² in Formula (H1) can be cited for other than that,

Φ is an n-valent aryl ring (preferably an n-valent benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a benzofluorene ring, a phenalene ring, a phenanthrene ring or a triphenylene ring), and n is It is an integer from 1 to 4, and

At least one hydrogen in the pyrene derivative may be substituted with deuterium.

The pyrene derivative represented by the formula (H4) can be prepared using a known raw material and a known synthesis method.

<Other host materials>

Other host materials include, for example, metal chelated oxinoid compounds including tris(8-quinolinolato)aluminum, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, Coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perrinone derivatives, cyclopentadiene derivatives, thiadiazolopyridine derivatives, pyrrolopyrrole derivatives, fluorene derivatives, benzofluorene derivatives, in polymers, polyphenylene vinyl Lene derivatives, polyparaphenylene derivatives, polythiophene derivatives, and compounds described in the June 2004 issue of Chemical Industry, page 13, and references published therein, etc., which can be used in combination with the above-mentioned host material. can

<Dopant material>

Examples of the dopant material include amine-containing benzofluorene derivatives, amine-containing pyrene derivatives, amine-free pyrene derivatives, amine-containing chrysene derivatives, and amine-containing styryl derivatives.

<Amine-containing benzofluorene derivative as dopant material>

The amine-containing benzofluorene derivative is, for example, represented by the following formula (D1).

[Formula 37]

In the formula (D1),

R ¹¹ and R ¹² are each independently, alkyl (preferably C1-C12 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 aryl) ) and

Ar ¹¹ to Ar ¹⁴ are each independently an optionally substituted aryl (preferably an optionally substituted aryl having 6 to 30 carbon atoms), and Ar ¹¹ and Ar ¹³ or Ar ¹² and Ar ¹⁴ combine to form a ring can do, and

At least one hydrogen in the amine-containing benzofluorene derivative may be substituted with deuterium.

In addition, in the above formula (D1), _{an example in which two amino groups (-N(Ar) 2} ) are substituted is shown. An amine-containing benzofluorene derivative in which one of them is a hydrogen atom, that is, an amino group (-N(Ar) _{2 )} ) may be an amine-containing benzofluorene derivative in which only one is substituted.

Ar ¹¹ to Ar ¹⁴ are each independently an optionally substituted aryl (preferably an optionally substituted aryl having 6 to 30 carbon atoms), and all of Ar ¹¹ to Ar ¹⁴ may be different or the same. Preferred aryl is C6-C18 aryl, More preferably, it is C6-C14 aryl, More preferably, it is C6-C12 aryl.

Specific examples of “aryl having 6 to 30 carbon atoms” include phenyl which is a monocyclic aryl, (1-,2-)naphthyl which is a condensed bicyclic aryl, acenaphthylene-(1-,3-,4-, 5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4- ,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2-,5- )yl, perylene-(1-,2-,3-)yl which is condensed pentacyclic aryl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

Preferred "C6-C30 aryl" includes phenyl, naphthyl, phenanthryl, glycenyl or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl. , and particularly preferably phenyl, 1-naphthyl or 2-naphthyl.

Ar ¹¹ and Ar ¹³ or Ar ¹² and Ar ¹⁴ may combine to form a ring. For example, when Ar ¹¹ and Ar ¹³ (or Ar ¹² and Ar ¹⁴ ) are phenyl groups, they combine to form amine-containing benzo A carbazole ring is formed including "N (nitrogen atom)" in the fluorene derivative, and when one or both are naphthyl groups, a benzocarbazole ring or a dibenzocarbazole ring is formed.

Although it will not specifically limit as a substituent to "C6-C30 aryl" as long as a desired characteristic is obtained, Preferably, alkyl, cycloalkyl, aryl, substituted silyl, cyano, and fluorine are mentioned.

Specific substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, n -alkyl, such as heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; aryl such as phenyl, biphenylyl, naphthyl, terphenylyl and phenanthryl; Methylphenyl, ethylphenyl, s-butylphenyl, t-butylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1,6-dimethylnaphthyl, 2,6-dimethylnaphthyl, 4-t-butylnaphthyl alkylaryl such as; cyano; Fluorine etc. are mentioned.

When two substituents are alkyl groups and are substituted with Ar ¹¹ (or Ar ¹² to Ar ¹⁴ ), they may combine to form a ring, and the ring may include, for example, a cyclopentane ring or a cyclohexane ring. can be heard

When the substituent is "substituted silyl", three hydrogens in the silyl group are each independently methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, and those substituted with phenyl, biphenylyl or naphthyl.

Specific examples of "substituted silyl" include trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tris-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, and isopropyldimethyl Silyl, butyldimethylsilyl, s-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, s-butyldiethylsilyl, t-butyldi Ethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, s-butyldipropylsilyl, t-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, and trialkylsilyls such as s-butyldiisopropylsilyl and t-butyldiisopropylsilyl. In addition, phenyldimethylsilyl, phenyldiethylsilyl, phenyldit-butylsilyl, methyldiphenylsilyl, ethyldiphenylsilyl, propyldiphenylsilyl, isopropyldiphenylsilyl, butyldiphenylsilyl, s-butyldiphenylsilyl , t-butyldiphenylsilyl, triphenylsilyl, and the like.

The "alkyl having 1 to 12 carbon atoms" in R ¹¹ and R ^{12 may be linear or branched.} That is, straight-chain alkyl having 1 to 12 carbon atoms or branched chain alkyl having 3 to 12 carbon atoms. More preferably, it is C1-C6 alkyl (C3-C6 branched alkyl), More preferably, it is C1-C4 alkyl (C3-C4 branched alkyl). 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, 4-methyl-2-pentyl, 3,3-dimethylbutyl or 2-ethylbutyl, etc. are mentioned, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl is preferred, more preferably methyl, isopropyl or t-butyl.

Specific examples of "cycloalkyl having 3 to 12 carbon atoms" for R ¹¹ and R ¹² include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, and cyclooctyl. Or dimethylcyclohexyl etc. are mentioned. Among these, cyclopentyl or cyclohexyl is preferable.

As "aryl having 6 to 30 carbon atoms" in R ¹¹ and R ¹² , the specific description may be given in the column of ^{Ar 11} to Ar ^{14 above.}

The amine-containing benzofluorene derivative represented by the formula (D1) can be prepared using a known raw material and a known synthesis method.

<Amine-containing pyrene derivative as dopant material>

The amine-containing pyrene derivative is, for example, represented by the following formula (D2).

[Formula 38]

In the formula (D2),

R ¹¹ to R ¹⁸ are each independently hydrogen, optionally substituted alkyl (preferably optionally substituted alkyl having 1 to 12 carbon atoms), optionally substituted cycloalkyl (preferably optionally substituted alkyl having 3 carbon atoms) ~12 cycloalkyl), optionally substituted aryl (preferably optionally substituted aryl having 6 to 30 carbon atoms), or optionally substituted heteroaryl (preferably optionally substituted 5 to 30 ring atoms) heteroaryl),

Ar ¹¹ to Ar ¹⁴ are each independently, optionally substituted aryl (preferably optionally substituted aryl having 6 to 30 carbon atoms), or optionally substituted heteroaryl (preferably the number of optionally substituted ring atoms) 5-30 heteroaryl), and,

At least one hydrogen in the amine-containing pyrene derivative may be substituted with deuterium.

In the formula (D2), two amino groups (-N(Ar) ₂ ) are substituted, but an amine-containing pyrene derivative in which one of them is a hydrogen atom, that is, an amino group (-N(Ar) ₂ ) It may be an amine-containing pyrene derivative substituted with only one.

"Aryl" of "optionally substituted aryl" in Ar ¹¹ to Ar ¹⁴ is aryl having 6 to 30 carbon atoms, preferred "aryl" is aryl having 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms is the aryl of

Specific examples of "aryl" include phenyl which is monocyclic aryl, (1-,2-)naphthyl which is condensed bicyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl which is condensed tricyclic aryl; Fluorene-(1-,2-,3-,4-,9-)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4-,9-)phenan Triphenyl, condensed tetracyclic aryl, triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalen-(1-,2-,5-)yl, condensed pentacyclic and perylene-(1-,2-,3-)yl and pentacene-(1-,2-,5-,6-)yl which are type aryl.

Particularly preferred "aryl" in Ar ¹¹ to Ar ¹⁴ is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl and phenanthryl, among these, phenyl, 4-biphenylyl, 1- Naphthyl, 2-naphthyl are preferred.

"Heteroaryl" of "optionally substituted heteroaryl" in Ar ¹¹ to Ar ¹⁴ is heteroaryl having 5 to 30 ring atoms, and preferred "heteroaryl" is heteroaryl having 5 to 24 ring atoms and more preferably heteroaryl having 5 to 18 ring atoms, and particularly preferably heteroaryl having 5 to 12 ring atoms.

In addition, the "heteroaryl" includes, for example, a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring member. For example, an aromatic heterocyclic group, etc. can be heard

As "heterocyclic group", for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl , pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, iso Quinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiadinyl, phenazinyl, indolizinyl and the like, and imidazolyl, pyridyl, carbazolyl and the like are preferable.

As "aromatic heterocyclic group", for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl , triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triadinyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzo[b]thienyl, dibenzothiophenyl , indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, pr thalazinyl, naphthylidinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiadinyl, phenazinyl, phenoxathynyl, thiantrenyl, indolizinyl, and the like; , thienyl, imidazolyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl and the like are preferable.

The "alkyl" of the "optionally substituted alkyl" in R ¹¹ to R ^{18 may be either a straight chain or a branched chain.} That is, straight-chain alkyl having 1 to 12 carbon atoms or branched chain alkyl having 3 to 12 carbon atoms. More preferably, it is C1-C6 alkyl (C3-C6 branched alkyl), More preferably, it is C1-C4 alkyl (C3-C4 branched alkyl). 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, 4-methyl-2-pentyl, 3,3-dimethylbutyl or 2-ethylbutyl, etc. are mentioned, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl is preferred, more preferably methyl, isopropyl or t-butyl.

"Cycloalkyl" of "cycloalkyl which may be substituted" in R ¹¹ to R ¹⁸ is cycloalkyl having 3 to 12 carbon atoms, and preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

R ¹¹ to R ¹⁸ as “optionally substituted aryl” and “optionally substituted heteroaryl”, for specific descriptions thereof, the description in the Ar ¹¹ to Ar ¹⁴ column may be cited.

Examples ^{of the substituent of "which may be substituted" in Ar 11} to Ar ¹⁴ and R ¹¹ to R ¹⁸ include alkyl, cycloalkyl, aryl, substituted silyl, cyano, and fluorine. , those described in the column of “alkyl” and “cycloalkyl” for ^{R 11} to R ¹⁸ , respectively, and those described in the column of “aryl” for ^{Ar 11} to Ar ^{14, respectively.}

Ar ¹¹ to Ar ¹⁴ and R ¹¹ to R ¹⁸ preferably have no “substituent”, but when they have a substituent, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s -Butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, n-undecyl, alkyl such as n-dodecyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; aryl such as phenyl, biphenylyl, naphthyl, terphenylyl and phenanthryl; Methylphenyl, ethylphenyl, s-butylphenyl, t-butylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1,6-dimethylnaphthyl, 2,6-dimethylnaphthyl, 4-t-butylnaphthyl alkylaryl such as; cyano; Fluorine etc. are mentioned.

When two "substituents" are alkyl groups and are substituted with Ar ¹¹ (or Ar ¹² to Ar ¹⁴ ), they may combine to form a ring, and the ring includes, for example, a cyclopentane ring or a cyclohexane ring. and the like.

In the case of "substituted silyl" as a substituent of "which may be substituted", three hydrogens in the silyl group are each independently methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, cyclo and those substituted with butyl, cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl.

Specific examples of "substituted silyl" include trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tris-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, and isopropyldimethyl Silyl, butyldimethylsilyl, s-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, s-butyldiethylsilyl, t-butyldi Ethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, s-butyldipropylsilyl, t-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, and trialkylsilyls such as s-butyldiisopropylsilyl and t-butyldiisopropylsilyl. In addition, phenyldimethylsilyl, phenyldiethylsilyl, phenyldit-butylsilyl, methyldiphenylsilyl, ethyldiphenylsilyl, propyldiphenylsilyl, isopropyldiphenylsilyl, butyldiphenylsilyl, s-butyldiphenylsilyl , t-butyldiphenylsilyl, triphenylsilyl, and the like.

Ar ¹¹ to Ar ¹⁴ and R ¹¹ to R ¹⁸ preferably do not have a “substituent”, but when they have a substituent, the number of substituents is, for example, the maximum substitutable number, preferably 1 to 3, More preferably, it is 1-2 pieces, More preferably, it is 1 piece. Further, at least one hydrogen in the amine-containing pyrene derivative may be substituted with deuterium.

The amine-containing pyrene derivative represented by the formula (D2) can be prepared using a known raw material and a known synthesis method.

<Amine-free pyrene derivative as dopant material>

The amine-free pyrene derivative is, for example, represented by the following formula (D3).

[Formula 39]

In the formula (D3),

R ¹¹ to R ¹⁶ can refer to the description ^{of R 11} to R ¹⁸ in formula (D2),

~ Ar ¹¹ Ar ¹⁴ is, it is possible to cite the description of Ar ¹¹ ~ Ar ¹⁴ in the formula (D2), and,

At least one hydrogen in the amine-free pyrene derivative may be substituted with deuterium.

The amine-free pyrene derivative represented by the formula (D3) can be prepared using a known raw material and a known synthesis method.

<Amine-containing chrysene derivative as dopant material>

The amine-containing chrysene derivative is, for example, represented by the following formula (D4).

[Formula 40]

In the formula (D4),

R ¹¹ to R ¹⁸ can refer to the description ^{of R 11} to R ¹⁸ in formula (D2),

~ Ar ¹¹ Ar ¹⁴ is, it is possible to cite the description of Ar ¹¹ ~ Ar ¹⁴ in the formula (D2), and,

At least one hydrogen in the amine-containing chrysene derivative may be substituted with deuterium.

_{In addition, although an example in which two amino groups (-N(Ar) 2} ) are substituted is shown in the above formula (D4), an amine-containing chrysene derivative in which either one is a hydrogen atom, that is, an amino group (-N(Ar) ₂ ) It may be an amine-containing chrysene derivative in which only one is substituted.

The amine-containing chrysene derivative represented by the above formula (D4) can be prepared using a known raw material and a known synthesis method.

<Amine-containing styryl derivative as dopant material>

The amine-containing styryl derivative is, for example, represented by the following formula (D5).

[Formula 41]

In the formula (D5),

Ar ¹¹ to Ar ¹⁴ are each, independently, optionally substituted aryl or optionally substituted heteroaryl,

Ar ¹⁵ to Ar ¹⁷ are each independently an optionally substituted arylene or an optionally substituted heteroarylene,

l, m, and n are each independently an integer of 1 to 3, p is an integer of 0 to 2,

When l is 2 or more, Ar ¹⁵ may be the same or different,

When m is 2 or more, Ar ¹⁶ may be the same or different,

When p is 1 or more and n is 2 or more, Ar ¹⁷ may be the same or different,

When p is 2 or more and n is 1, Ar ¹⁷ may be the same or different,

A substituent of Ar ¹¹ to Ar ¹⁷ is halogen, alkyl, aryl, heteroaryl, optionally substituted silyl or cyano.

In addition, in the formula (D5), two amino groups (-N(Ar) ₂ ) are substituted, but an amine-containing styryl derivative in which one of them is a hydrogen atom, that is, an amino group (-N(Ar) ₂ ) It may be an amine-containing styryl derivative in which only one is substituted.

Ar ¹¹ - may heteroaryl which may be optionally substituted aryl, and optionally substituted with at the Ar ^17, the expression (D2) can be cited to the description of Ar ¹¹ to Ar ¹⁴ in the substituents of Ar ¹¹ to Ar ¹⁷ As the phosphorus alkyl, aryl, heteroaryl and optionally substituted silyl, those described as the substituents for ^{Ar 11} to Ar ¹⁴ and R ¹¹ to R ^{18 in formula (D2) can be cited.}

More specific amine-containing styryl derivatives are, for example, those represented by the following formula (D6).

[Formula 42]

In the formula (D6),

~ Ar ¹¹ Ar ^14, the Ar ¹¹ in the formula ~ Ar ¹⁴ in (D2) may cite an explanation, and

At least one hydrogen in the amine-containing styryl derivative may be substituted with deuterium.

In the formula (D6), an example in which two amino groups (-N(Ar) ₂ ) are substituted is shown, but an amine-containing styryl derivative in which either one is a hydrogen atom, that is, an amino group (-N(Ar) ₂ ) It may be an amine-containing styryl derivative in which only one is substituted.

The amine-containing styryl derivatives represented by the formulas (D5) and (D6) can be prepared using known raw materials and known synthesis methods.

Other amine-containing styryl derivatives include, for example, N,N,N',N'-tetra(4-biphenylyl)-4,4'-diaminostilbene, N,N,N',N '-tetra(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-tetra(2-naphthyl)-4,4'-diaminostilbene, N, N'-di(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene, N,N'-di(9-phenanthryl)-N,N'-diphenyl- 4,4'-diaminostilbene, 4,4'-bis[4"-bis(diphenylamino)styryl]-biphenyl, 1,4-bis[4'-bis(diphenylamino)styryl ]-Benzene, 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-dimethylfluorene, 4,4'-bis(9-ethyl-3-carbazovinylene)- Biphenyl, 4,4'-bis(9-phenyl-3-carbazolene)-biphenyl, etc. are mentioned. In addition, amine-containing styryl derivatives described in Japanese Patent Application Laid-Open No. 2003-347056 and Japanese Patent Application Laid-Open No. 2001-307884 can also be used.

<Other dopant materials>

Other dopant materials include, for example, perylene derivatives, borane derivatives, aromatic amine derivatives and coumarin derivatives, and compounds described in the June 2004 issue of Chemical Industry, page 13, and references published therein. , can also be used in combination with the dopant material described above.

Examples of the perylene derivative include 3,10-bis(2,6-dimethylphenyl)perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenyl Perylene, 3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3-(1'-pyrenyl) -8,11-di(t-butyl)perylene, 3-(9'-anthryl)-8,11-di(t-butyl)perylene, 3,3'-bis(8,11-di( t-butyl)perylenyl) and the like. In addition, Japanese Patent Laid-Open No. H11-97178, Japanese Patent Application Laid-Open No. 2000-133457, Japanese Patent Application Laid-Open No. 2000-26324, Japanese Patent Application Laid-Open No. 2001-267079, Japanese Patent Application Laid-Open No. 2001-267078, Japanese Patent Laid-Open The perylene derivatives described in Japanese Patent Application Laid-Open No. 2001-267076, Japanese Patent Application Laid-Open No. 2000-34234, Japanese Patent Application Laid-Open No. 2001-267075, and Japanese Patent Application Laid-Open No. 2001-217077 can also be used.

As the borane derivative, for example, 1,8-diphenyl-10-(dimethylbolyl)anthracene, 9-phenyl-10-(dimethylbolyl)anthracene, 4-(9'-anthryl)di Mesitylbolylnaphthalene, 4-(10'-phenyl-9'-anthryl)dimethylbolylnaphthalene, 9-(dimethylbolyl)anthracene, 9-(4'-biphenylyl)-10-(di mesitylbolyl)anthracene, 9-(4'-(N-carbazolyl)phenyl)-10-(dimethylbolyl)anthracene, etc. are mentioned. In addition, the borane derivative described in International Publication No. 2000/40586 and the like can also be used.

As the aromatic amine derivative, for example, N,N,N,N-tetraphenylanthracene-9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis( 4-di(1-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamino-9-(4-di- p-Tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6-diphenylamino-2 -naphthyl) anthracene, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenyl Amine, [6-(4-diphenylamino-phenyl)naphthalen-2-yl]-diphenylamine, 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl, 4,4' -Bis[6-diphenylaminonaphthalen-2-yl]biphenyl, 4,4"-bis[4-diphenylaminonaphthalen-1-yl]-p-terphenyl, 4,4"-bis[6- and diphenylaminonaphthalen-2-yl]-p-terphenyl. In addition, the aromatic amine derivative described in Japanese Patent Application Laid-Open No. 2006-156888 and the like can also be used.

Examples of the coumarin derivative include coumarin-6 and coumarin-334. In addition, the coumarin derivatives described in Japanese Patent Application Laid-Open No. 2004-43646, Japanese Patent Application Laid-Open No. 2001-76876, and Japanese Patent Application Laid-Open No. H6-298758 can also be used.

7. Organic EL minor electron injection layer and electron transport layer

The electron injection layer 107 serves to efficiently inject electrons moving from the cathode 108 into the electron transport layer 106 . The electron transport layer 106 serves to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting auxiliary layer 110 . . The electron transport layer 106 and the electron injection layer 107 are respectively formed by laminating and mixing one or two or more of the electron transporting/injecting material, or a mixture of the electron transporting/injecting material and the polymer binder.

The electron injection/transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting electrons, and it is preferable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable that the material is a material having high electron affinity, high electron mobility, excellent stability, and which trap impurities do not easily occur during manufacture and use. However, when the hole-electron transport balance is considered, the luminous efficiency is improved even if the electron transport capacity is not very high, when the main role is to effectively block the flow of the holes from the anode to the cathode side without recombination. It has the same effect as a material with high electron transport ability. Accordingly, the electron injection/transport layer in the present embodiment may also include a function of a layer capable of effectively blocking the movement of holes.

In the present invention, since electrons from the electron transport layer are transported to the light emitting layer through the light emission auxiliary layer, electron transport from the electron transport layer to the light emission auxiliary layer is stagnant, so that the electron injection property into the light emitting layer is greatly reduced. As the electron-hole recombination is reduced, the density of triplet excitons is reduced, and the collision frequency of triplet excitons is reduced, so that the TTF phenomenon does not occur efficiently. If the electron injection from the electron transport layer to the light emitting auxiliary layer is greatly damaged, electrons are accumulated in the electron transport layer, resulting in a high voltage, and there is a possibility that the stored electrons collide with triplet excitons and energy is changed.

Since the benzofluorene compound and the fluorene compound as a material for the light emitting auxiliary layer according to the present invention have a relatively large affinity A _a derived from the specific structure described above, they are generally used as electron transport materials for organic EL devices. For most materials, the electron injection property from the electron transport layer to the light emitting layer is not greatly reduced or inhibited.

Furthermore, in order to efficiently inject electrons from the electron transport layer to the light emitting layer, the present invention is not limited to a specific principle, but as for the electron transport material, the affinity A _{e is the affinity A a} of the light emitting auxiliary layer material, and A _a >A It is preferable to select one that satisfies the relation of _{e -0.8 eV.} This relationship, A _a> It is more preferred that it is more preferable to satisfy A _e -0.6eV, and satisfies _{A a>} A _e -0.5eV.

<Material for electron transport layer>

As the material for the electron transport layer, a heterocyclic compound is preferable, and examples thereof include pyridine derivatives, thiazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, phenanthroline derivatives and phosphine oxide derivatives. . In addition, these materials can also be used as a material for an electron injection layer.

<Pyridine derivative as material for electron transport layer>

The pyridine derivatives are, for example, those represented by the following formulas (ET1) to (ET3).

[Formula 43]

In the formula (ET1),

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

In the above formula (ET2),

R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 alkyl) of aryl),

In the above formula (ET3),

R ¹¹ and R ¹² are each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 alkyl) of aryl), and R ¹¹ and R ¹² may be combined to form a ring,

In the above formulas (ET1) to (ET3),

“Pyridine-based substituent” is any one of the following formulas (Py-1) to (Py-15), and each of the pyridine-based substituents may be independently substituted with alkyl having 1 to 4 carbon atoms, and

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

In addition, one of the two "pyridine-based substituents" in the formulas (ET2) and (ET3) may be substituted with aryl.

[Formula 44]

The "alkyl" for R ¹¹ to R ¹⁸ may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. Preferred "alkyl" is C1-C18 alkyl (C3-C18 branched chain alkyl). A more preferable "alkyl" is C1-C12 alkyl (C3-C12 branched alkyl). A more preferable "alkyl" is C1-C6 alkyl (C3-C6 branched alkyl). A particularly preferable "alkyl" is C1-C4 alkyl (C3-C4 branched alkyl).

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

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

Examples of the “cycloalkyl” for R ¹¹ to R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

As ^{"aryl" for R 11} to R ¹⁸ , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, still more preferably aryl having 6 to 14 carbon atoms, particularly preferred Preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of “aryl having 6 to 30 carbon atoms” include phenyl which is a monocyclic aryl, (1-,2-)naphthyl which is a condensed bicyclic aryl, acenaphthylene-(1-,3-,4-, 5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenanthrene-(1-,2-)yl, (1-,2-,3-,4- ,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthalene-(1-,2-,5- )yl, perylene-(1-,2-,3-)yl which is condensed pentacyclic aryl, pentacene-(1-,2-,5-,6-)yl, etc. are mentioned.

Preferred "C6-C30 aryl" includes phenyl, naphthyl, phenanthryl, glycenyl or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl. , and particularly preferably phenyl, 1-naphthyl or 2-naphthyl.

^{R 11} and R ¹² in the formula (ET3) may combine to form a ring, and as a result, the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, Fluorene, indene, or the like may be spiro-bonded.

In the formulas (ET1) to (ET3), the “pyridine-based substituent” may be any one of the formulas (Py-1) to (Py-15), but among them, the following formula (Py-21) It is preferable that it is any one of formula (Py-44).

[Formula 45]

The pyridine derivatives represented by the above formulas (ET1) to (ET3) can be prepared using known raw materials and known synthesis methods.

<A thiazole derivative and a benzothiazole derivative as a material for an electron transport layer>

The thiazole derivative is, for example, represented by the following formula (ET4).

[Formula 46]

The benzothiazole derivative is, for example, represented by the following formula (ET5).

[Formula 47]

In the formula (ET4) or (ET5),

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

The "thiazole-based substituent" and "benzothiazole-based substituent" are those in which the pyridyl group in the "pyridine-based substituent" in the above formulas (ET1) to (ET3) is substituted with a thiazole group or a benzothiazole group,

At least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.

[Formula 48]

[phi] is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be exemplified by the formula (ET2) or (ET3), wherein R ¹¹ to R ¹⁸ in each formula is the formula (ET2) or (ET3) can be cited. In the above formulas (ET2) or (ET3), two pyridine-based substituents are described in a combined form, but when these are substituted with a thiazole-based substituent (or a benzothiazole-based substituent), both pyridine-based substituents are thiazole-based substituents (or a benzothiazole-based substituent) may be substituted (that is, n=2), or one pyridine-based substituent is substituted with a thiazole-based substituent (or a benzothiazole-based substituent), and the other pyridine-based substituent is R ¹¹ to R ¹⁸ can also be substituted with (i.e., n=1). ^{Further, for example, at least one of R 11} to R ¹⁸ in the formula (ET2) may be substituted with a thiazole-based substituent (or a benzothiazole-based substituent) to replace the “pyridine-based substituent” with R ¹¹ to R ¹⁸ . may be

The thiazole derivatives or benzothiazole derivatives represented by the formulas (ET4) and (ET5) can be prepared using known raw materials and known synthesis methods.

<Benzoimidazole derivative as material for electron transport layer>

Benzoimidazole is, for example, represented by the following formula (ET6).

[Formula 49]

In the above formula (ET6),

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

The "benzoimidazole-based substituent" is a pyridyl group in the "pyridine-based substituent" in the formulas (ET1) to (ET3) substituted with a benzimidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

[Formula 50]

^{R 11} in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 30 carbon atoms, in the formulas (ET2) and (ET3) The description of R ¹¹ may be cited.

[phi] is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be exemplified by the formula (ET2) or (ET3), wherein R ¹¹ to R ¹⁸ in each formula is the formula (ET2) or (ET3) can be cited. In addition, in the above formula (ET2) or (ET3), two pyridine-based substituents are described in a combined form, but when they are substituted with a benzimidazole-based substituent, both pyridine-based substituents may be substituted with a benzimidazole-based substituent. Alternatively (ie, n=2), one pyridine-based substituent may be substituted with a benzimidazole-based substituent and the other pyridine-based substituent ^{may be substituted with R 11} to R ¹⁸ (ie, n=1). ^{Further, for example, at least one of R 11} to R ¹⁸ in the formula (ET2) may be substituted with a benzimidazole-based substituent, and the “pyridine-based substituent” may be substituted ^{with R 11} to R ^{18 .}

The benzoimidazole derivative represented by the formula (ET6) can be prepared using known raw materials and known synthesis methods.

Specific examples of benzimidazole derivatives include 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10-(naphthalene) -2-yl) anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl) -1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole, 1 -(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di(naphthalene-) 2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) Phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d ]Imidazole.

<Phenanthroline derivative as material for electron transport layer>

A phenanthroline derivative is, for example, represented by the following formula (ET7) or (ET8).

[Formula 51]

In the above formula (ET8),

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

In the above formulas (ET7) and (ET8),

R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 alkyl) of aryl),

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

Alkyl, cycloalkyl and aryl in R ¹¹ ~ R ^18, can be cited for explanation of R ¹¹ ~ R ¹⁸ in the formula (ET1). In addition, phi other than what was mentioned above is mentioned, for example, the thing of the following structural formulas. In addition, each R in the following structural formula is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

[Formula 52]

The phenanthroline derivative represented by the above formula (ET7) or (ET8) can be prepared using a known raw material and a known synthesis method.

Specific examples of the phenanthroline derivative include 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) Lin-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline-5-yl), bathocuproine (basocuproin) or 1,3-bis(2-phenyl) -1,10-phenanthroline-9-yl)benzene and the like.

<Phosphine oxide derivative as material for electron transport layer>

The phosphine oxide derivative is, for example, represented by the following formula (ET9).

[Formula 53]

In the formula (ET9), R ¹ to R ³ may be the same or different, and are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, It is selected from condensed rings formed between an aryl ether group, an arylthioether group, an aryl group, a heterocyclic group, a halogen, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an amino group, a nitro group, a silyl group, and an adjacent substituent.

Ar ¹ and Ar ² may be the same or different, and are an aryl group or a heteroaryl group. However, ^{at least one of Ar 1} and Ar ² has a substituent or forms a condensed ring between adjacent substituents. n is an integer of 1 to 3, and when n is 3, R ¹ does not exist.

Among these substituents, the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, and may be unsubstituted or substituted. There is no restriction|limiting in particular in the substituent in the case of being substituted, For example, an alkyl group, an aryl group, a heterocyclic group, etc. are mentioned, This point is common also to the following description. In addition, carbon number of an alkyl group is although it does not specifically limit, From the point of availability and cost, it is the range of 1-20 normally.

In addition, a cycloalkyl group represents, for example, saturated alicyclic hydrocarbon groups, such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, and it does not matter whether it is unsubstituted or substituted. Although carbon number of an alkyl group part is not specifically limited, Usually, it is the range of 3-20.

In addition, an aralkyl group represents, for example, the aromatic hydrocarbon group via aliphatic hydrocarbons, such as a benzyl group and a phenylethyl group, even if both an aliphatic hydrocarbon and an aromatic hydrocarbon are unsubstituted, it may be substituted. Although carbon number of an aliphatic part is not specifically limited, Usually, it is the range of 1-20.

In addition, an alkenyl group represents, for example, the unsaturated aliphatic hydrocarbon group containing double bonds, such as a vinyl group, an allyl group, a butadienyl group, and this may be unsubstituted or substituted. Although carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.

In addition, a cycloalkenyl group represents, for example, the unsaturated alicyclic hydrocarbon group containing double bonds, such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexene group, It does not matter whether it is unsubstituted or substituted.

In addition, an alkynyl group shows, for example, the unsaturated aliphatic hydrocarbon group containing triple bonds, such as an acetylenyl group, even if it is unsubstituted, it does not matter even if it is substituted. Although carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.

In addition, the alkoxy group represents, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. Although carbon number of an alkoxy group is not specifically limited, Usually, it is the range of 1-20.

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

In addition, the aryl ether group represents, for example, an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted. Although carbon number of an aryl ether group is not specifically limited, Usually, it is the range of 6-40.

In the arylthioether group, the oxygen atom of the ether bond of the arylether group is substituted with a sulfur atom.

In addition, an aryl group shows aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, and a pyrenyl group, for example. The aryl group may be unsubstituted or substituted. Although carbon number of an aryl group is not specifically limited, Usually, it is the range of 6-40.

In addition, the heterocyclic group represents, for example, a cyclic structural group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group, which may be unsubstituted or substituted. Does not matter. Although carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-30.

Halogen represents fluorine, chlorine, bromine, and iodine.

The aldehyde group, carbonyl group, and amino group may include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

In addition, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a heterocyclic ring may be unsubstituted, and may be substituted.

The silyl group represents, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. Although carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20. In addition, the number of silicon is 1-6 normally.

Condensed rings formed between adjacent substituents include, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , Ar ¹ and Ar To form a conjugated or non-conjugated condensed ring between ^{2 and the like.} Here, when n is 1, two R ¹ may form a conjugated or non-conjugated condensed ring. These condensed rings may contain nitrogen, oxygen, and sulfur atoms in their intracyclic structure, and may further be condensed with other rings.

The phosphine oxide derivative represented by the formula (ET9) can be prepared using a known raw material and a known synthesis method.

<Other electron transport materials>

As other materials used for the electron transport layer and the electron injection layer, arbitrarily selected from compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used for electron injection layers and electron transport layers of organic EL devices. Available. It can also be used together with the material for electron-transporting layers mentioned above.

Specifically, naphthalene derivatives, anthracene derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, thiophene derivatives, thiadiazole derivatives, Quinoxaline derivatives, quinoxaline derivative polymers, benzazole compounds, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, imidazopyridine derivatives, benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives , aldazine derivatives, carbazole derivatives, indole derivatives, bisstyryl derivatives, and the like. In addition, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), triazole derivatives (N-naphthyl-2,5-di phenyl-1,3,4-triazole, etc.), benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthylidin-2-yl)phenylphosphine oxide etc.) etc. are mentioned. Although these materials are used individually, you may mix and use with different materials.

A metal complex having electron-accepting nitrogen may also be used, for example, a quinolinol-based metal complex or a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, or a flavonol metal complex. and a benzoquinoline metal complex. Although these materials are used individually, you may mix and use with different materials.

The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

[Formula 54]

In the formula, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

Specific examples of the quinolinol-based metal complex include 8-quinolinollithium, tris(8-quinolinolate)aluminum, tris(4-methyl-8-quinolinolate)aluminum, tris(5-methyl- 8-quinolinolate)aluminum, tris(3,4-dimethyl-8-quinolinolate)aluminum, tris(4,5-dimethyl-8-quinolinolate)aluminum, tris(4,6-dimethyl -8-quinolinolate)aluminum, bis(2-methyl-8-quinolinolate)(phenolate)aluminum, bis(2-methyl-8-quinolinolate)(2-methylphenolate)aluminum , Bis(2-methyl-8-quinolinolate)(3-methylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(4-methylphenolate)aluminum, bis(2-methyl -8-quinolinolate)(2-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2-methyl-8-quinolinol rate)(4-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,3-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2 ,6-Dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,4-dimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3,5 -Dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2 ,6-diphenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,4,6-triphenylphenolate)aluminum, bis(2-methyl-8-quinolinolate) (2,4,6-trimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,4,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8- Quinolinolate)(1-naphtolate)aluminum, bis(2-methyl-8-quinolinolate)(2-naphtolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)( 2-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(4- Phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3,5-dimethylphenolate)alu Min, 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-quinolinol rate)aluminum, bis(2-methyl-4-ethyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolate)aluminum, bis(2- Methyl-4-methoxy-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-quinolinolate)aluminum, bis(2-methyl-5-cyano -8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolate)aluminum, bis(2-methyl-5-trifluoromethyl-8-qui Nolinolate) aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolate)aluminum, bis(10-hydroxybenzo[h]quinoline)beryllium, etc. are mentioned. .

The electron transport layer or the electron injection layer may further contain a material capable of reducing the material forming the electron transport layer or the electron injection layer. Various types of reducing substances are used as long as they have a certain reducing property. For example, alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides (eg LiF, etc.), alkali At least one selected from the group consisting of oxides of earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals can be used suitably.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV) or Cs (work function 1.95 eV), and Ca (work function 2.9 eV). , Sr (work function 2.0 to 2.5 eV) or Ba (work function 2.52 eV), etc. are mentioned, and those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb, or Cs, More preferably, it is Rb or Cs, Most preferable is Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of light emission and the lifetime of the organic EL device can be improved. In addition, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination including Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and a combination of Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by addition to the material forming the electron transport layer or the electron injection layer, the luminance of light emission and the lifespan of the organic EL device can be improved.

8. Organic EL element's cathode

The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injection layer 107 , the electron transport layer 106 , and the light emission auxiliary layer 110 .

The material for forming the cathode 108 is not particularly limited as long as it is a material capable of efficiently injecting electrons into the organic layer, but the same material as the material for forming the anode 102 may be used. Among them, metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy) , magnesium-indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, etc.) are preferable. In order to increase electron injection efficiency and improve device characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, these low work function metals are generally unstable in the atmosphere in many cases. In order to improve this point, for example, a method of using an electrode with high stability by doping a trace amount of lithium, cesium, or magnesium into an organic layer 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.

Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride, hydrocarbon A preferred example of laminating a high molecular compound or the like is exemplified. The manufacturing method of these electrodes is also not restrict|limited in particular as long as it can take conduction|electrical_connection, such as resistance heating, an electron beam, sputtering, ion plating, and coating.

9. Organic EL How to make a device

Each layer constituting the organic EL device is formed by coating the material constituting each layer using a vapor deposition method, resistance heating deposition, electron beam deposition, sputtering, molecular lamination method, inkjet method, or printing method, spin coating method or casting method, or coating method. It can be formed by setting it as a thin film by such a method. There is no limitation in particular about the film thickness of each layer formed in this way, Although it can set suitably according to the property of a material, Usually, it is the range of 2 nm - 5000 nm. The film thickness can be usually measured with a crystal oscillation type film thickness measuring device or the like.

For example, in the case of forming a thin film using a vapor deposition method, the deposition conditions differ depending on the type of material, the target crystal structure and association structure of the film, and the like. In general, deposition conditions, a boat heating temperature is + 50 ~ + 400 ℃, the degree of vacuum 10 ^-6 ~ 10 ^-3 Pa, vapor deposition rate of 0.01 ~ 50nm / second, substrate temperature of -150 ~ + 300 ℃, the range of film thickness of 2nm ~ 5μm It is desirable to set it appropriately.

In addition, for example, in the case of an inkjet printing method, that is, a method of forming each layer of an organic EL device using a solution containing an organic EL material, a good solvent is selected for the organic EL material, and the uniform solution is adjusted and used. It is also possible to use a poor solvent, or it is also possible to prepare and use a dispersion using a mixed solvent of a good solvent and a poor solvent. However, in order to suppress the nozzle clogging of an inkjet head, it is preferable to use a good solvent. For example, examples of many good solvents include aromatic solvents, halogen solvents, and etheric solvents. Examples of poor solvents include alcohol solvents, ketone solvents, paraffinic solvents, or 4 carbon atoms. and the above alkylbenzene derivatives. More specifically, many examples of good solvents include aromatic solvents such as toluene, xylene, and mesitylene, halogen-based solvents such as chlorobenzene, and ether-based solvents such as diphenyl ether, which are poor solvents. As many of them, alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol, which are straight chain or branched alcohols having 1 to 20 carbon atoms, benzyl alcohol derivatives, and alkylbenzene derivatives such as hydroxyalkylbenzene derivatives, straight-chain or branched butylbenzene, dodecylbenzene, tetralin, and cyclohexylbenzene. The amount of the solvent to be used can be appropriately prepared in consideration of the amount and type of the organic EL material, the thickness of the organic thin film layer, and the like.

Next, as an example of a method of manufacturing an organic EL device, an organic EL device comprising an anode/hole injection layer/hole transport layer/ a light emitting layer made of a host material and a dopant material/a light emitting auxiliary layer/electron transport layer/electron injection layer/cathode will be described. On a suitable substrate, a thin film of an anode material is formed 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, and a light emitting auxiliary layer, an electron transport layer and an electron injection layer are formed on the light emitting layer. By doing so, the target organic EL device is obtained. In addition, in the manufacture of the above-described organic EL device, the cathode, electron injection layer, electron transport layer, light emitting auxiliary layer, light emitting layer, hole transport layer, hole injection layer, and the anode can be manufactured in this order by reversing the manufacturing order. do.

When a DC voltage is applied to the organic EL device obtained in this way, it is enough to apply the positive polarity to the positive electrode and the negative polarity to the negative electrode. and both) can be observed. In addition, this organic EL element emits light even when a pulse current or an alternating current is applied. In addition, the waveform of the alternating current to be applied may be arbitrary.

10. Organic EL minor Application example

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

As a display device, flexible displays, such as a panel display, such as a color flat panel display, and a flexible color organic EL display, etc. are mentioned, for example (For example, Unexamined-Japanese-Patent No. H10-335066, Japanese Patent Laid-Open 2003) -321546, Japanese Patent Laid-Open No. 2004-281086, etc.). In addition, as a display method of a display, a matrix and/or a segment method etc. are mentioned, for example. In addition, the matrix display and the segment display may coexist in the same panel.

A matrix means that pixels for display are two-dimensionally arranged, such as a grid shape or a mosaic shape, and a character or an image is displayed as a set of pixels. The shape or size of the pixel is determined depending on the application. For example, a square pixel having a side of 300 μm or less is usually used for displaying images and characters on a computer, monitor, and television, and in the case of a large display such as a display panel, a pixel with a side of the order of mm is used. In case of black and white display, pixels of the same color may be arranged, but in case of color display, pixels of red, green, and blue are displayed side by side. In this case, there are typically a delta type and a stripe type. Incidentally, the matrix driving method may be either a line-sequential driving method or an active matrix. The linear sequential driving has an advantage that it has a simple structure. Considering the operating characteristics, the active matrix may be excellent, so it is necessary to use this separately according to the purpose.

In the segment method (type), a pattern is formed to display predetermined information, and the determined area is made to emit light. For example, time and temperature display in digital clocks and thermometers, operation status display of audio equipment and electronic cookers, etc., and panel display of automobiles, etc. are mentioned.

Examples of the lighting device include lighting devices such as indoor lighting, backlights of liquid crystal display devices, etc. See Patent Publication No. 2004-119211, etc.). A backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a watch, an audio device, an automobile panel, a display panel, a display, and the like. In particular, considering that it is difficult to reduce the thickness of a liquid crystal display device because it is made of a fluorescent lamp or a light guide plate in a conventional method as a backlight for computer use, in which thickness reduction is a problem, the backlight using the organic EL device according to the present embodiment is a thin type backlight. and lightweight.

Example

<Synthesis example of material for light auxiliary layer>

Hereinafter, Formula (2-1) - Formula (2-5), Formula (2-21), Formula (2-41), Formula (2-61), Formula (2-62), Formula (2-85) , Formula (2-87), Formula (1-1), Formula (1-71), Formula (3-5), Formula (3-6), Formula (3-8) Formula (5-7), Synthesis examples of compounds represented by formulas (6-9) and (EAL-1) will be described. In addition, compound (EAL-1) is a comparative compound.

<Synthesis example of compound (2-1)>

[Formula 55]

Under nitrogen atmosphere, 7,7-diphenyl-5,9-bis(trifluoromethanesulfonyloxy)-7H-benzo[c]fluorene (6.66g), 2-naphthyleneboronic acid (5.16g) Dissolved in a mixed solvent of tetrahydrofuran and isopropyl alcohol (100 ml, tetrahydrofuran / isopropyl alcohol = 1/4 (volume ratio)), tetrakis (triphenylphosphine) palladium (0) (1.16 g) The mixture was added and stirred for 5 minutes, after which potassium phosphate (12.7 g) was added and refluxed for 4 hours. After the reaction, 50 ml of the solvent was removed. 100 ml of water was added, and the precipitate was filtered. The precipitate was washed again with water and methanol to obtain a crude product of compound (2-1). The crude product was subjected to column purification with silica gel (solvent: heptane/toluene = 3/1 (volume ratio)), followed by sublimation purification to obtain 5.0 g (yield: 80.5%) of the target compound (2-1).

The structure of compound (2-1) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.93 (d,1H), 8.53 (d,1H), 8.06-8.04 (m,2H), 7.93-7.21 (m,28H).

<Synthesis example of compound (2-2)>

[Formula 56]

Under nitrogen atmosphere, 5,9-dibromo-7,7-diphenyl-7H-benzo [c] fluorene (2.2 g), 1-naphthylene boronic acid (1.6 g), tetrakis (triphenylphosphine) ) Palladium (0) (Pd(PPh ₃ ) ₄ ) (0.1 g), potassium phosphate (3.6 g) and toluene (21 ml) were placed in a flask and stirred for 5 minutes. Then, water (4 ml) was added and refluxed for 4 hours. After completion of heating, the reaction solution was cooled, and water (10 ml) was added. The reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the drying agent was removed, and the solvent was distilled off under reduced pressure. Thereafter, recrystallization is performed with ethyl acetate and further purification is performed by sublimation, and the target compound (2-2) "5,9-di(naphthalen-1-yl)-7,7-diphenyl-7H-benzo[c] ]fluorene" was obtained in 0.8 g (yield: 31%).

The structure of compound (2-2) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.96(d,1H), 8.56(d,1H), 7.94-7.84(m,5H), 7.69-7.63(m,4H), 7.57-7.26(m,15H) ), 7.20~7.17(m,6H).

<Synthesis example of compound (2-3)>

[Formula 57]

In a nitrogen atmosphere, 5,9-dibromo-7,7-diphenyl-7H-benzo [c] fluorene (5.26 g) and 4-biphenylboronic acid (4.36 g) were dissolved in a mixed solvent of toluene and ethanol ( 50 ml, toluene/ethanol = 4/1 (volume ratio)), tetrakis (triphenylphosphine) palladium (0) (0.69 g) was added, stirred for 5 minutes, and then 20 ml of 2M aqueous sodium carbonate solution was added and refluxed for 8 hours. After completion of heating, the reaction mixture was cooled, and the organic layer was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solid obtained by removing the drying agent and distilling off the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane/toluene = 3/1 (volume ratio)), followed by sublimation purification to obtain 3.9 of the target compound (2-3). g (yield: 58%) was obtained.

The structure of compound (2-3) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.91(d,1H), 8.49(d,1H), 8.11(d,1H), 7.79-7.77(m,2H), 7.73-7.20(m,31H).

<Synthesis example of compound (2-4)>

[Formula 58]

Under nitrogen atmosphere, 5,9-dibromo-7,7-diphenyl-7H-benzo[c]fluorene (2.2g), 9-phenanlenboronic acid (9-fenanlenboronic acid) (2.3g) , tetrakis (triphenylphosphine) paldium (0) (Pd (PPh ₃ ) ₄ ) (0.1 g), potassium phosphate (3.6 g) and toluene (21 ml) were placed in a flask and stirred for 5 minutes. Then, water (4 ml) was added and refluxed for 4 hours. After completion of heating, the reaction solution was cooled, and water (20 ml) was added. The reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the drying agent was removed, the solvent was distilled off under reduced pressure, and column purification was performed with silica gel (solvent: heptane/toluene = 3/1 (volume ratio)). Again, by sublimation purification, the target compound (2-4) "5,9-di(phenanlen-9-yl)-7,7-diphenyl-7H-benzo[c]fluorene" was 1.6 g (yield: 53%) was obtained.

The structure of compound (2-4) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.99(d,1H), 8.80-8.76(m,3H), 8.72(d,1H), 8.61(d,1H), 7.97(d,1H), 7.92~ 7.87(q,2H), 7.77~7.60(m,13), 7.51~7.48(m,2H), 7.40~7.33(m,6H), 7.21~7.17(m,6H).

<Synthesis example of compound (2-5)>

[Formula 59]

First, methanesulfonic acid (130 mL) was added to compound (2-5a) "5-methoxy-2-(4-methoxynaphthalen-1-yl)-benzoic acid methyl ester" (21.0 g) under a nitrogen atmosphere, , and heated and stirred at 65 °C for 1.5 hours. The reaction mixture was added to ice water, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid (22.5 g) was purified by recrystallization (solvent: ethyl acetate) to obtain an intermediate compound (2-5c) (14.6 g) (yield 77%).

Next, 2 prepared using 2-bromobiphenyl (17.0 g), magnesium (1.77 g) and THF (150 mL) in a THF (120 mL) suspension of the intermediate compound (2-5c) (13.2 g) under a nitrogen atmosphere. - A THF solution of biphenylmagnesium bromide was added dropwise at 0°C, followed by heating and stirring again at reflux temperature for 1.5 hours. Water was added to the reaction mixture, the target component was extracted with toluene, and the organic layer was concentrated to obtain a solid product (25.4 g) of the target component. The obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 9/1 (volume ratio)) to obtain an intermediate compound (2-5e) (17.4 g) (yield 86%).

Then, concentrated sulfuric acid (0.1 mL) was added to a suspension of the intermediate compound (2-5e) (17.4 g) in acetic acid (230 mL) at room temperature under a nitrogen atmosphere, followed by heating and stirring at 100°C for 3 hours. Water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was washed with methanol to obtain an intermediate compound (2-5f1) (16.2 g) (yield 97%).

Then, to a dichloromethane (250 mL) solution of the intermediate compound (2-5f1) (16.2 g) under a nitrogen atmosphere, 1 mol/L boron tribromide/dichloromethane solution (100 mL) was added dropwise at 0 ° C. The mixture was stirred at room temperature again overnight. Water was added to the reaction mixture, the target component was extracted with ethyl acetate, and the organic layer was concentrated to obtain a solid product of the target component. The obtained solid was washed with heptane to obtain an intermediate compound (2-5f2) (15.1 g) (yield 100%).

Then, to a pyridine (200 mL) solution of the intermediate compound (2-5f2) (15.1 g) under a nitrogen atmosphere, trifluoromethanesulfonic anhydride (32.2 g) was added dropwise at 0° C., and then again overnight at room temperature. stirred. Water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography (developing solvent: toluene), and intermediate compound (2-5f3) "5,9-bis(trifluoromethanesulfonyloxy)-7H-benzo[c]fluorene- 7-spiro-9'-fluorene" (23.6 g) was obtained (yield 94%).

Finally, under nitrogen atmosphere, intermediate compound (2-5f3) (6.63 g), 2-naphthylene boronic acid (3.78 g), potassium phosphate (12.7 g), tetrahydrofuran (20 mL) and isopropyl alcohol (80 mL) To the mixed solution of tetrakis(triphenylphosphine)paldium (0) (1.16 g) was added, and the mixture was heated and stirred at reflux temperature for 7.5 hours. Water was added to the reaction mixture, the target component was extracted with toluene, and the organic layer was concentrated to obtain a solid product (8.90 g) of the target component. The obtained solid was purified by silica gel column chromatography (developing solvent: heptane/toluene = 2/1 (volume ratio)) and recrystallization (solvent: ethyl acetate) to obtain compound (2-5) (2.28 g) (yield 37) %).

The glass transition temperature (Tg) of the obtained compound was 164°C. Furthermore, the structure of the obtained compound (2-5) was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=6.86-6.87(m,3H), 7.12-7.17(m,3H), 7.37-753(m,8H), 7.62-7.64(dd,1H), 7.76-7.93 (m,12H), 8.02~8.04(d,1H), 8.58~8.60(d,1H), 8.99~9.01(d,1H).

<Synthesis example of compound (2-21)>

[Formula 60]

First, an intermediate compound (2-21a) obtained by Suzuki coupling of 1-naphthaleneboronic acid and 2-bromo-5-chlorobenzoic acid methyl ester was synthesized. By reacting the obtained intermediate compound (2-21a) with lithiation of 2-bromonaphthalene with n-butyllithium to obtain the intermediate compound (2-21b), and further cyclizing with sulfuric acid, the intermediate compound ( 2-21c) was obtained. By brominating the obtained intermediate compound (2-21c) with NBS, the intermediate compound (2-21d) "5-bromo-9-chloro-7,7-di(naphthalen-2-yl)-7H-benzo [c] flu"Oren" was obtained.

Then, under nitrogen atmosphere, intermediate compound (2-21d) (3.82 g), 2-naphthalene boronic acid (2.48 g), Pd (dba) 2 (0.38 g), tricyclohexyl phosphine (0.28 g), ginseng phosphate A flask containing potassium (8.40 g), toluene (24 ml), ethanol (6 ml) and water (3 ml) was heated and stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, the precipitated precipitate was collected by suction filtration, and the obtained precipitate was washed with water. After purification by activated carbon column chromatography (toluene) again, 1.78 g (yield 39%) of the target compound (2-21) was obtained by recrystallization from a mixed solvent of toluene/IPA=1.

<Synthesis example of compound (2-41)>

[Formula 61]

Under nitrogen atmosphere, 5,9-dibromo-7,7-dimethyl-7H-benzo [c] fluorene (6.00 g), 2-naphthalene boronic acid (5.65 g), potassium carbonate (6.19 g), tetrabutyl A mixed solution of ammonium bromide (TBAB) (0.96 g), Pd(PPh ₃ ) ₂ Cl ₂ (0.31 g), toluene (30 ml) and water (15 mL) was heated and stirred at reflux temperature for 3 hours. Water was added to the reaction mixture, the target component was extracted with toluene, and the organic layer was concentrated. The obtained solid was purified by silica gel column chromatography (developing solvent: heptane/toluene = 3/1 (volume ratio)) and washed again with ethyl acetate to obtain 1.60 g (yield 22%) of compound (2-41).

<Synthesis example of compound (2-61)>

[Formula 62]

Under nitrogen atmosphere, 5-bromo-7,7-diphenyl-7H-benzo [c] fluorene (2.3 g), bis (pinacolato) diboron (1.3 g), [1,1'-bis ( Diphenylphosphino) ferrocene] dichloropaldium (II) (0.4 g), potassium acetate (3.0 g) and dimethyl sulfoxide (50 ml) were placed in a flask and heated at 80° C. for 5 hours. Then, return to room temperature, 5-bromo-7,7-diphenyl-7H-benzo [c] fluorene (1.8 g), bis (pinacolato) diboron (0.15 g), [1,1' -Bis(diphenylphosphino)ferrocene]dichloropaldium(II) (0.15 g) was added, and the mixture was further heated at 80°C for 12 hours. After completion, the reaction solution was cooled, and water (50 ml) was added. The reaction mixture was extracted with toluene, the solvent was distilled off under reduced pressure, and the crude product obtained was subjected to short column purification with silica gel (solvent: toluene). Thereafter, purification was performed by column purification with silica gel (solvent: toluene/heptane = 1/4 (volume ratio)). After removing the solvent with a vacuum pump, sublimation purification was performed again to obtain 0.7 g (yield 20%) of the target compound (2-61).

<Synthesis example of compound (2-62)>

[Formula 63]

First, the intermediate compound (2-62a) obtained by Suzuki coupling of 1-naphthaleneboronic acid and 2-bromo-5-chlorobenzoic acid methyl ester is reacted with phenyl lithium to obtain an intermediate compound (2-62b), and then sulfuric acid was cyclized to obtain an intermediate compound (2-62c) "9-chloro-7,7-diphenyl-7H-benzo [c] fluorene".

Then, under nitrogen atmosphere, intermediate compound (2-62c) (3.0 g), bispinacolatodiboron (0.95 g), Pd(dba) ₂ (0.21 g), tricyclohexylphosphine (0.21 g), ginseng phosphate A flask containing potassium (4.74 g) and dimethoxyethane (15 ml) was heated and stirred at reflux temperature for 2 and a half hours. After confirming that the bispinacolatodiboron was consumed, xylene (30.0 ml) was added, and dimethoxyethane was removed while refluxing. After heating and stirring again at reflux temperature for 9 hours, the reaction solution was cooled to room temperature, methanol was added, the precipitated precipitate was collected by suction filtration, and the obtained precipitate was washed with water. After purification by silica gel short-pass column (chlorobenzene) again, the target compound (2-62) was obtained by recrystallization from toluene, 0.79 g (yield 37%).

<Synthesis example of compound (2-85)>

[Formula 64]

First, 7,7-diphenyl-7H-benzo [c] fluorene is brominated with NBS, and the obtained intermediate compound (2-85a) is reacted with bispinacolatodiboron to obtain an intermediate boronic acid ester (2-85b) "2-(7,7-dimethyl-7H-benzo[c]fluoren-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane" was obtained.

Then, under nitrogen atmosphere, intermediate compound (2-85b) (4.00 g), 4,4'-dibromo-1,1'-biphenyl (1.69 g), Pd-132 (0.15 g), tripotassium phosphate (2.87 g), TBAB (0.17 g), toluene (40 ml), and a mixed solution of water (5 ml) was heated and stirred at reflux temperature for 4 and a half hours. The reaction solution was cooled to room temperature, the precipitated precipitate was collected by suction filtration, and the obtained precipitate was washed with water and methanol. By recrystallizing from orthodichlorobenzene again, 0.52 g (yield 15%) of the target compound (2-85) was obtained.

<Synthesis example of compound (2-87)>

[Formula 65]

Under nitrogen atmosphere, the intermediate compound (2-85b) (4.00 g), 2,6-dibromonaphthalene (1.40 g), Pd-132 (0.07 g), tripotassium phosphate (2.61 g), toluene (40 ml) , a mixed solution of isopropanol (10 ml) and water (5 ml) was heated and stirred at reflux temperature for 4 and a half hours. The reaction solution was cooled to room temperature, the precipitated precipitate was collected by suction filtration, and the obtained precipitate was washed with water and methanol. After re-precipitation from a chlorobenzene/ethyl acetate mixed solvent, the target compound (2-87) was obtained by recrystallization from orthodichlorobenzene, 1.43 g (yield: 48%).

<Synthesis example of compound (1-1)>

[Formula 66]

Under nitrogen atmosphere, 2,7-dibromo-9,9-diphenyl-9H-fluorene (3.00 g), 2-naphthaleneboronic acid (2.38 g), potassium carbonate (2.61 g), TBAB (0.20 g) , Pd(PPh ₃ ) ₂ Cl ₂ (0.13 g), a mixed solution of toluene (30 ml) and water (15 mL) was heated and stirred at reflux temperature for 2 hours. Water was added to the reaction mixture, the target component was extracted with toluene, and the organic layer was concentrated. The crystals precipitated during concentration were collected by suction filtration and recrystallized from chlorobenzene to obtain 0.57 g (yield 16%) of the target compound (1-1).

<Synthesis example of compound (1-71)>

[Formula 67]

A commercially available product (product number LT-E411 BSBF) manufactured by OHJEC Corporation was used.

<Synthesis example of compound (3-5)>

[Formula 68]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2009-184993.

<Synthesis example of compound (3-6)>

[Formula 69]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2009-184993.

<Synthesis example of compound (3-8)>

[Formula 70]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2009-184993.

<Synthesis example of compound (5-7)>

[Formula 71]

First, under a nitrogen atmosphere, 1-hydroxy-2-methyl naphthoate (25 g) was dissolved in dichloromethane (200 ml). After pyridine (15 ml) was added, the mixture was cooled to -20°C, and trifluoromethanesulfonic anhydride (44 g) was added. After stirring at room temperature for 10 hours, water was added to the reaction mixture to precipitate with dichloromethane. The extract was concentrated and purified by silica gel column (toluene/heptane=2/1 (volume ratio)). The solvent was removed to obtain 28 g (yield 67%) of the intermediate compound (5-7a).

Then, in a nitrogen atmosphere, the intermediate compound (5-7a) (8.7 g) and 1-naphthylene boronic acid (5.0 g) were dissolved in a mixed solvent of toluene and water (100 ml, toluene/water = 1/1 (volume ratio)). Then, tetrakis (triphenylphosphine) palladium (0) (1.0 g) and potassium phosphate (14.5 g) were added and refluxed for 6 hours. After the reaction, water was removed and the solution was concentrated. The crude product was subjected to column purification with silica gel (solvent: ethyl acetate/toluene = 1/10 (volume ratio)) to obtain 5.7 g (yield: 70%) of an oily intermediate compound (5-7b).

Then, the intermediate compound (5-7b) (5.7 g) was dissolved in tetrahydrofuran (100 ml) under a nitrogen atmosphere, and cooled to -70°C. A phenyllithium/dibutyl ether solution (2.0 mol/ml) (45 ml) was added, and the mixture was stirred at room temperature for 10 hours. After the reaction, an excess of phenyl lithium was quenched by adding an aqueous ammonium chloride solution. The organic layer was collected and concentrated, and column purification was performed with silica gel (solvent: toluene) to obtain 5.1 g (yield: 67%) of an oily intermediate compound (5-7c).

Next, the intermediate compound (5-7c) (5.1 g) was dissolved in acetic acid (50 ml), a few drops of concentrated sulfuric acid were added, and the mixture was heated and stirred at 80°C for 1 hour. The crude product precipitated by adding water was subjected to column purification with silica gel (solvent: toluene) to obtain 3.6 g (yield: 73%) of the intermediate compound (5-7d) as a white solid.

Then, the intermediate compound (5-7d) (3.6 g) was dissolved in a mixed solvent of acetic acid/dichloromethane (100 ml, acetic acid/dichloromethane = 1/1 (volume ratio)) under a nitrogen atmosphere, and zinc chloride (3.1 g) was added and heated at 55 °C. A benzyltrimethylammonium tribromide/dichloromethane solution (10.6 g/25 ml) was added dropwise from the dropping funnel, followed by stirring at 55° C. for 5 hours. Water was added to the reaction mixture, followed by extraction with chloroform. The crude product from which the solvent was removed under reduced pressure was subjected to column purification with silica gel (solvent: toluene/heptane = 1/1 (volume ratio)) to obtain 2.8 g (yield 52%) of the intermediate compound (5-7e) as a pale yellow solid.

Finally, in a nitrogen atmosphere, the intermediate compound (5-7e) (2.8 g) and phenylboronic acid (1.3 g) were dissolved in a mixed solvent of toluene / ethanol (50 ml, toluene / ethanol = 4/1 (volume ratio)) and , tetrakis (triphenylphosphine) palladium (0) (1.0 g) and sodium carbonate aqueous solution (4.1 g/20 ml) were added, and the mixture was refluxed for 6 hours. After the reaction, water was added to dissolve the salt, and the organic layers were collected and the solution was concentrated. The crude product was subjected to column purification with silica gel (solvent: toluene). After recrystallization from toluene again, sublimation purification was carried out, and 0.58 g of the target compound (5-7) "5,7,7,9-tetraphenyl-7H-dibenzo[c,g]fluorene" was added (yield 20%). ) was obtained.

<Synthesis example of compound (6-9)>

[Formula 72]

First, in a nitrogen atmosphere, the intermediate compound (5-7a) (8.7 g) and 2-naphthylene boronic acid (5.0 g) were dissolved in a mixed solvent of toluene/ethanol/water (50ml/15ml/15ml (volume ratio)), Tetrakis (triphenylphosphine) palladium (0) (1.0 g) and potassium phosphate (14.5 g) were added and refluxed for 6 hours. After the reaction, water was removed and the solution was concentrated. The crude product was subjected to column purification with silica gel (solvent: heptane/toluene = 1/1 (volume ratio)) to obtain 8.0 g (yield 99%) of an oily intermediate compound (6-9a).

Then, the intermediate compound (6-9a) (8.0 g) was dissolved in tetrahydrofuran (80 ml) under a nitrogen atmosphere, and cooled to -70°C. A phenyllithium/dibutyl ether solution (2.0 mol/ml) (38 ml) was added, and the mixture was stirred at room temperature for 10 hours. After the reaction, an excess of phenyl lithium was quenched by adding an aqueous ammonium chloride solution. The organic layer was collected and concentrated, and the crude product was subjected to column purification with silica gel (solvent: toluene) to remove the solvent. 9.3 g (yield 96%) of the intermediate compound (6-9b) was obtained as a white solid.

Next, the intermediate compound (6-9b) (9.3 g) was dissolved in acetic acid (50 ml), a few drops of concentrated sulfuric acid were added, and the mixture was heated and stirred at 80°C for 1 hour. The solid precipitated by adding water was washed with an aqueous sodium hydrogen carbonate solution, water and methanol to obtain 8.8 g (yield 99%) of the intermediate compound (6-9c) as a white solid.

Then, the intermediate compound (6-9c) (3.3 g) was dissolved in a mixed solvent of acetic acid/chloroform (100 ml, acetic acid/chloroform = 2/3 (volume ratio)) under a nitrogen atmosphere, and zinc chloride (1.3 g) was added. and cooled to -30°C. After adding benzyltrimethylammonium tribromide (3.4g), the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, followed by extraction with chloroform. The crude product from which the solvent was removed under reduced pressure was subjected to column purification with silica gel (solvent: toluene) to obtain 3.5 g (yield 92%) of the intermediate compound (6-9d) as a pale yellow solid.

Finally, in a nitrogen atmosphere, the intermediate compound (6-9d) (2.7 g) and 2-naphthyl boronic acid (1.0 g) were mixed with toluene/ethanol in a mixed solvent (50 ml, toluene/ethanol = 4/1 (volume ratio)) , tetrakis (triphenylphosphine) palladium (0) (0.1 g) and sodium carbonate aqueous solution (2.3 g / 10 ml) were added and refluxed for 6 hours. After the reaction, water was added to dissolve the salt, and the organic layers were collected and the solution was concentrated. The crude product was subjected to column purification with silica gel (solvent: toluene/heptane = 1/4 (volume ratio)). After recrystallization from toluene again, sublimation purification was carried out to obtain 1.0 g (yield 33%) of the target compound (6-9).

<Synthesis example of comparative compound (EAL-1)>

[Formula 73]

It was synthesized by the synthesis method described in International Publication No. 2010/074087.

<Synthesis example of host material>

Hereinafter, the synthesis example of the compound represented by a formula (BH-1) - a formula (BH-5) is demonstrated.

<Synthesis example of compound (BH-1)>

[Formula 74]

The compound represented by the formula (BH-1) is compound 1 (see page 4 of the publication) described in Korean Patent Application Laid-Open No. 10-2010-0007552 (published on January 22, 2010), and is a known compound . The compound represented by the formula (BH-1) was synthesized with reference to the synthesis method described in the publication.

<Synthesis example of compound (BH-2)>

[Formula 75]

The compound represented by the formula (BH-2) is compound H1 (see page 10 of the publication) described in International Publication No. 2007/065548 (published on June 14, 2007), and is a known compound. The compound represented by the formula (BH-2) was synthesized with reference to the synthesis method described in the publication.

<Synthesis example of compound (BH-3)>

[Formula 76]

First, under a nitrogen atmosphere, naphthalene-2,7-diyl bis(trifluoromethanesulfonate) (31.8 g), 2-naphthalene boronic acid (12.9 g), tetrakis (triphenylphosphine) palladium (0) (Pd(PPh ₃ ) ₄ ) (1.73 g), potassium phosphate (31.8 g) and a mixed solvent of tetrahydrofuran (THF) and isopropyl alcohol (IPA) (300 ml, THF/IPA=4/1 (volume ratio)) was placed in a flask and refluxed for 5 hours. After completion of heating, the reaction solution was cooled, water was added, and the target component was extracted with toluene. Again, the crude product obtained by concentrating the organic layer under reduced pressure was subjected to column purification with silica gel (solvent: heptane), and 13.4 g of [2,2'-binaphthalen]-7-yl trifluoromethanesulfonate as an intermediate compound (yield: 44) %) was obtained.

Then, under a nitrogen atmosphere, [2,2'-binaphthalen]-7-yl trifluoromethanesulfonate (10 g), (10-phenylanthracen-9-yl) boronic acid (7.4 g), tetrakis (tri Phenylphosphine) palladium (0) (0.57 g, Pd (PPh ₃ ) ₄ ), potassium phosphate (10.55 g), and a mixed solvent of toluene and ethanol (100 ml, toluene/ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Then, 10 ml of water was added and refluxed for 3 hours. After the heating was completed, the reaction solution was cooled, 60 ml of methanol was added, and the precipitate was filtered off. The precipitate was washed again with methanol and water to obtain a crude product of the target compound represented by the formula (BH-3). The crude product was subjected to short column purification with silica gel (solvent: toluene), then washed with a mixed solvent of methanol and ethyl acetate (methanol/ethyl acetate = 4/1 (volume ratio)), recrystallized from toluene, and sublimated again. Purification was carried out to obtain 6.6 g (yield: 53%) of 9-([2,2'-binaphthalen]-7-yl)-10-phenylanthracene as the target (BH-3) compound.

The structure of the target compound (BH-3) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.24(s,1H), 8.22(s,1H), 8.15~8.08(q,2H), 8.08(s,1H), 8.02~7.89(m,5H), 7.78~7.73(m,4H), 7.65~7.50(m,8H), 7.37~7.31(m,4H).

The glass transition temperature (Tg) of the target compound (BH-3) was 116.0°C.

[Measuring device: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: cooling rate 200℃/Min., heating rate 10℃/Min.]

<Synthesis example of compound (BH-4)>

[Formula 77]

As the compound represented by the formula (BH-4), commercially available from Luminescence Technology Corp. (product name: LT-N473 m-Bpye, Tg=97°C in product information) was used.

<Synthesis example of compound (BH-5)>

[Formula 78]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2012-104806.

<Synthesis example of dopant material>

Hereinafter, the synthesis example of the compound represented by Formula (BD-1) - Formula (BD-8) is demonstrated.

<Synthesis example of compound (BD-1)>

[Formula 79]

In a nitrogen atmosphere, 5,9-dibromo-7,7-dimethyl-7H-benzo [C] fluorene (9.5 g) and aniline (4.5 g) were dissolved in dehydrated toluene (80 ml), and bis (dibenzyl) Lidenacetone) palladium (140 mg), sodium t-butoxide (7.0 g), and tris (t-butyl) phosphine (0.15 g) were added and heated at 50° C. for 2 hours. After the reaction, 1-bromo-4-(trimethylsilyl)benzene (11 g), palladium acetate (27 mg), and sodium t-butoxide (7.0 g) were added, and heating was performed at 80°C for 4 hours. 100 ml of water was added, and the organic layer was washed with water using a separatory funnel. After removing the aqueous layer, the organic layers were collected and concentrated using a rotary evaporator to obtain a crude product. The crude product was subjected to column purification with silica gel (solvent: heptane/toluene = 5/1 (volume ratio)), followed by sublimation purification to obtain 3.1 g (yield 18%) of compound (BD-1).

The structure of compound (BD-1) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.68(d,1H), 8.15(d,1H), 8.05(d,1H), 7.56(t,1H,J=8Hz), 7.45-6.94(m,32H) ), 1.41(s,6H), 0.27(s,9H), 0.22(s,9H).

<Synthesis example of compound (BD-2)>

[Formula 80]

In a nitrogen atmosphere, 5,9-dibromo-7,7-dimethyl-7H-benzo [C] fluorene (8.0 g) and p-methylaniline hydrochloride (5.7 g) were dissolved in dehydrated toluene (200 ml), Bis(dibenzylideneacetone)paldium (115mg), sodium t-butoxide (15g), and 4-(dimethylamino)phenyl)bist-butylphosphine (0.160g) were added and heated at 80°C for 2 hours. did. After the reaction, 1-bromo-4-(trimethylsilyl)benzene (10 g) was added, and heating was performed at 80°C for 4 hours. Here, 100 ml of water was added, and the organic layer was washed with water using a separatory funnel. After removing the aqueous layer, the organic layers were collected and concentrated using a rotary evaporator to obtain a crude product. The crude product was subjected to column purification with alumina (solvent: heptane/toluene = 5/1 (volume ratio)), followed by sublimation purification to obtain 6.9 g of compound (BD-2) (yield 46%).

The structure of compound (BD-2) was confirmed by NMR measurement.

¹ H-NMR (Toluene-d8): δ=8.67 (d,1H), 8.30 (d,1H), 8.00 (d,1H), 7.52 (t,1H,J=8Hz), 7.42-6.83 (m, 20H), 2.13(s,3H), 2.06(s,3H), 1.16(s,6H), 0.24(s,9H), 0.20(s,9H).

<Synthesis example of compound (BD-3)>

[Formula 81]

In an argon atmosphere, 5,9-diiodo-7,7-dimethyl-7H-benzo[C]fluorene (6.1 g) and aniline (2.3 g) were dissolved in dehydrated xylene (100 ml), and palladium bis (dibenzylidene) (0.12 g), sodium t-butoxide (7.2 g) and (4-(dimethylamino)phenyl)di-t-butylphosphine (0.16 g) were added and heated at 70° C. for 2 hours. Then, 1-bromo-naphthalene (5.2 g) was added thereto, and the mixture was heated at 100° C. for 3 hours. After cooling to room temperature, 100 ml of water was added, and the organic layer was washed with water using a separatory funnel. After removing the aqueous layer, the organic layers were collected and concentrated using a rotary evaporator to obtain a crude product. The crude product was subjected to column purification with alumina (solvent: toluene) to remove color components, and then column purification was performed again with silica gel (solvent: toluene/heptane = 1/3 (volume ratio)). After recrystallization from toluene/heptane again, this was purified by sublimation to obtain 1.9 g (yield 23%) of compound (BD-3).

The structure of compound (BD-3) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.62(d,1H), 8.14(d,1H), 8.07(d,1H), 7.96(d,1H), 7.88(t,1H), 7.77(d, 1H), 7.66(d,1H), 7.52-6.73(m,25H), 1.27(s,6H).

<Synthesis example of compound (BD-4)>

[Formula 82]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2011-37837.

<Synthesis example of compound (BD-5)>

[Formula 83]

It was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2013-080961.

<Synthesis example of compound (BD-6)>

[Formula 84]

It was synthesized by the synthesis method described in US Patent Application Publication No. 2010-0141124.

<Synthesis example of compound (BD-7)>

[Formula 85]

It was synthesized by the synthesis method described in International Publication No. 2004/044088.

<Synthesis example of compound (BD-8)>

[Formula 86]

It was synthesized by the synthesis method described in International Publication No. 2002/020459.

<Synthesis example of electron transport material>

Hereinafter, the synthesis example of the compound represented by Formula (ETL-1) and Formula (ETL-6) is demonstrated.

<Synthesis example of compound (ETL-1)>

[Formula 87]

First, 2-chloroanthracene (5.00 g), phenylboronic acid (4.3 g), tris (dibenzylideneacetone) ipalladium (0) (538 mg), tricyclohexylphosphine (494 mg), tripotassium phosphate (9.98 g) ), and toluene (75 ml) were placed in a flask, and stirred for 2 hours at reflux under an argon atmosphere. After heating, 1.5 liters of toluene was added to the reaction solution, cooled to room temperature, filtered, and the filtrate was purified by silica gel column chromatography (mobile phase: toluene) using toluene as a moving bed. The solvent was distilled off under reduced pressure, and the concentrate was recrystallized from toluene to obtain 2-phenylanthracene (5.0 g).

Then, in a flask under a nitrogen atmosphere, 2-phenylanthracene (3.32 g) was dissolved in 400 ml of dichloromethane. There, 5.00 g of bromine dissolved in 30 ml of carbon tetrachloride was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction was stopped with an aqueous sodium thiosulfate solution. The organic layer was extracted with a separatory funnel and concentrated with an evaporator. The concentrate was recrystallized from toluene (50 ml) to obtain 9,10-dibromo-2-phenylanthracene (4.4 g).

Then, 9,10-dibromo-2-phenylanthracene (10.0 g), bis (pinacolato) diboron (14.8 g), bis (dibenzylideneacetone) palladium (0) (838 mg), tricyclo Hexylphosphine (1.02 g), potassium acetate (7.15 g) and 1,4-dioxane (50 ml) were placed in a flask, and stirred for 8 hours at reflux under an argon atmosphere. After completion of heating, toluene was added to the reaction solution, cooled to room temperature, filtered, and the filtrate was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography using toluene as a moving layer, and recrystallized from a tetrahydrofuran/heptane mixed solution, and 9,10-bis(4,4,5,5-tetramethyl-1, 3,2-dioxaborolanyl)-2-phenylanthracene (8.3 g) was obtained.

Finally, 9,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-2-phenylanthracene (0.80 g), 5-bromo-2,2 '-Bipyridine (0.83 g), tris (dibenzylideneacetone) ipalladium (0) (88 mg), tricyclohexyl phosphine (81 mg), tripotassium phosphate (1.36 g), and toluene (35 ml) were placed in a flask , under argon atmosphere, and stirred at reflux temperature for 27 hours and a half. After completion of heating, the reaction solution was cooled to room temperature, pure water was added, and the organic layer was extracted. The organic layer was concentrated by an evaporator, and the concentrate was purified by activated alumina column chromatography using toluene as a moving layer. Recrystallization was performed with a mixed solvent of chloroform/ethyl acetate to obtain the compound (ETL-1) "9,10-bis(2,2'-bipyridin-5-yl)-2-phenylanthracene" (198 mg).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=7.3(t,1H), 7.4(m,6H), 7.6(d,2H), 7.7(m,3H), 7.8(d,1H), 7.9(m, 3H), 8.0(m,2H), 8.6(d,2H), 8.7(d,2H), 8.8(m,2H), 8.9(m,2H).

<Synthesis example of compound (ETL-2)>

[Formula 88]

9,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-2-phenylanthracene (5.0 g), 4-(2-pyridyl)bromobenzene (5.0 g), tetrakis (triphenylphosphine) palladium (0) (0.57 g), toluene (20 ml), ethanol (7 mL), potassium carbonate aqueous solution (potassium carbonate 4.2 g - water 7 ml) were placed in a flask, The mixture was stirred for 14.5 hours at reflux under argon atmosphere. After completion of heating, the reaction solution was cooled to room temperature and filtered. The obtained crude product was washed with water and methanol, then recrystallized from chlorobenzene, and compound (ETL-2) "9,10-bis(4-(2-pyridyl)phenyl)-2-phenyl anthracene" (3.5 g). The glass transition temperature (Tg) of the obtained compound was 134°C.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.8(d,2H), 8.3(d,4H), 8.0-7.7(m,8H), 7.6-7.4(m,5H), 7.4(d,2H)7.4 ~7.3(m,7H).

<Synthesis example of compound (ETL-3)>

[Formula 89]

It was synthesized by the synthesis method described in International Publication No. 2012/060374.

<Synthesis example of compound (ETL-4)>

[Formula 90]

It was synthesized by the synthesis method described in International Publication No. 2010/137678.

<Synthesis example of compound (ETL-5)>

[Formula 91]

It was synthesized by the synthesis method described in International Publication No. 2003/060956.

<Synthesis example of compound (ETL-6)>

[Formula 92]

It was synthesized by the synthesis method described in International Publication No. 2004/080975.

Another fluorene compound, a benzofluorene compound, a dibenzofluorene compound, an indenotriphenylene compound, and an indenopyrene compound can be synthesized by a method similar to the above synthesis example by appropriately selecting the raw material compound.

<Characteristics when used in an electroluminescent device>

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

Examples 1-11, Examples 12-31 and Comparative Examples 1 to 6 the voltage (V), the light emitting wavelength (nm) characteristics at the time of manufacturing the organic EL device, each of 1000cd / m ² light emission according to, CIE chromaticity ( x, y), the external quantum efficiency (%) was measured, and then the time (h) for maintaining the ^{luminance of 80% (800 cd/m 2 ) or more of the initial luminance was measured.} In addition, in some examples, the time (h) for maintaining the luminance of 90% (900cd/m ^{2 ) or more of the initial luminance was measured.}

In addition, the quantum efficiency of the light emitting device includes an internal quantum efficiency and an external quantum efficiency. The internal quantum efficiency represents the ratio of the external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is purely converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of the photon emitted to the outside of the light emitting device, and a part of the photons generated in the light emitting layer is absorbed or continuously reflected inside the light emitting device, and the outside of the light emitting device is Since it cannot be emitted as a , the external quantum efficiency is lower than the internal quantum efficiency.

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

Table 1 below shows the material composition and EL characteristic data of each layer in the organic EL devices according to Examples 1 to 11 produced. In addition, the material composition and EL characteristic data of each layer in the organic EL devices according to Examples 12 to 31 and Comparative Examples 1 to 6 produced are shown in Table 2 below.

[Table 1]

[Table 2]

In Table 1, "HI" (the hole injection layer material) N ^4, N ^{4 '-} diphenyl -N ^4, N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1 ,1'-biphenyl]-4,4'-diamine, "HT" (hole transport layer material) is N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N- (4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine. The chemical structure is shown below.

[Formula 93]

<Example 1>

<Device using compound (2-1) as a light emitting auxiliary layer>

A glass substrate (manufactured by Opto Science, Inc.) of 26 mm × 28 mm × 0.7 mm in which ITO formed to a thickness of 180 nm by sputtering was polished to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), molybdenum vapor deposition boat containing HI (hole injection layer material), and molybdenum containing HT (hole transport layer material). Deposition boat, molybdenum vapor deposition boat containing BH-1, molybdenum vapor deposition boat containing BD-1, molybdenum vapor deposition boat containing compound (2-1), molybdenum vapor deposition boat containing ETL-1 A boat, a molybdenum vapor deposition boat containing LiF (electron injection layer material), and a molybdenum vapor deposition boat containing Al (cathode material) were installed.

Each of the following layers was sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is reduced to 5 × 10 ^-4 Pa, and first, a vapor deposition boat containing HI (hole injection layer material) is heated and vapor-deposited to a film thickness of 40 nm to form a hole injection layer, followed by HT (hole transport layer) material) was heated, and vapor-deposited to a film thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing BH-1 and the vapor deposition boat containing BD-1 were heated simultaneously, and vapor-deposited so that it might become a film thickness of 30 nm, and the light emitting layer was formed. The deposition rate was controlled so that the weight ratio of BH-1 and BD-1 was approximately 95:5. Then, the vapor deposition boat containing the compound (2-1) was heated and evaporated to a film thickness of 20 nm to form a light emitting auxiliary layer. Then, the deposition boat containing ETL-1 was heated and deposited to a film thickness of 10 nm to form an electron transport layer. Further, an electron injection layer was formed by heating a vapor deposition boat containing LiF (electron injection layer material) and depositing it to a film thickness of 1 nm. The above deposition rate was 0.01 to 1 nm/sec.

Thereafter, a vapor deposition boat containing Al (cathode material) was heated and vapor-deposited so as to have a film thickness of 100 nm to form a cathode. At this time, a cathode was formed so that the deposition rate was 0.1 to 10 nm, and an organic electroluminescent device was obtained.

Using the ITO electrode as the anode and the Al electrode as the cathode, applying a DC voltage to ^{measure the characteristics at 1000cd/m 2} light emission. As a result, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.120) was was obtained In addition, the driving voltage was 4.90V, and the external quantum efficiency was 5.61%. In addition, the time for maintaining the luminance of 80% (800 cd/m ^{2 ) or more of the initial luminance was 400 hours.}

<Example 2>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that ETL-1 as the material for the electron transport layer was changed to ETL-2. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 4.54V and the external quantum efficiency was 5.90%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 356 hours.

<Example 3>

<Device using compound (2-2) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-2). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 6.71V and the external quantum efficiency was 3.82%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 554 hours.

<Example 4>

<Device using compound (2-3) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-3). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 5.17V and the external quantum efficiency was 5.55%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 407 hours.

<Example 5>

<Device using compound (2-4) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-4). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 6.49V, and the external quantum efficiency was 4.03%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 335 hours.

<Example 6>

<Device using compound (2-5) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that compound (2-1) as a material for the light-emitting auxiliary layer was replaced with compound (2-5). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 5.08V, and the external quantum efficiency was 4.90%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 530 hours.

<Example 7>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that BH-1 as a host material was changed to BH-2. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.130) was obtained. In addition, the driving voltage was 5.07V, and the external quantum efficiency was 5.17%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 570 hours.

<Example 8>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that BH-1 as a host material was changed to BH-3. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 4.86V, and the external quantum efficiency was 5.15%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 591 hours.

<Example 9>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that BH-1 as a host material was changed to BH-3 and BD-1 as a dopant material was changed to BD-2. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 466 nm and CIE chromaticity (x, y) = (0.140, 0.200) was obtained. In addition, the driving voltage was 4.98V, and the external quantum efficiency was 5.43%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 748 hours.

<Example 10>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that BH-1 as a host material was changed to BH-3 and BD-1 as a dopant material was changed to BD-3. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission having a wavelength of 459 nm and CIE chromaticity (x, y) = (0.140, 0.150) was obtained. In addition, the driving voltage was 5.41V and the external quantum efficiency was 3.79%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 408 hours.

<Example 11>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 1 except that BH-1 as a host material was changed to BH-4. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 460 nm and CIE chromaticity (x, y) = (0.140, 0.140) was obtained. In addition, the driving voltage was 4.61V, and the external quantum efficiency was 6.20%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 312 hours.

<Example 12>

<Device using compound (2-1) as a light emitting auxiliary layer>

In the same manner as in Example 1, an organic electroluminescent device was obtained. Using the ITO electrode as the anode and the Al electrode as the cathode, applying a DC voltage to ^{measure the characteristics at 1000cd/m 2} light emission. As a result, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.143, 0.120) was obtained In addition, the driving voltage was 4.80V, and the external quantum efficiency was 6.42%. In addition, the time to maintain the luminance of 80% (800cd/m ^{2 ) or more of the initial luminance was 560 hours.}

<Comparative Example 1>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (EAL-1). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 453 nm and CIE chromaticity (x, y) = (0.143, 0.121) was obtained. In addition, the driving voltage was 3.72V, and the external quantum efficiency was 6.99%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 244 hours.

<Example 13>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that ETL-1 as the material for the electron transport layer was changed to ETL-5. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.143, 0.121) was obtained. In addition, the driving voltage was 5.95V and the external quantum efficiency was 5.12%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 463 hours.

<Example 14>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that ETL-1 as the material for the electron transport layer was changed to ETL-3. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.143, 0.118) was obtained. In addition, the driving voltage was 4.38V, and the external quantum efficiency was 7.40%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 155 hours.

<Example 15>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that ETL-1 as the material for the electron transport layer was changed to ETL-6. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.142, 0.117) was obtained. In addition, the driving voltage was 5.62V, and the external quantum efficiency was 5.96%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 232 hours.

<Example 16>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-6, respectively. ^{As a result of measuring the characteristics at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 457 nm and CIE chromaticity (x, y) = (0.139, 0.099) was obtained. In addition, the driving voltage was 4.74V, and the external quantum efficiency was 5.44%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 219 hours.

<Example 17>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-4, respectively. ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 460 nm and CIE chromaticity (x, y) = (0.139, 0.143) was obtained. In addition, the driving voltage was 4.99V, and the external quantum efficiency was 6.74%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 500 hours.

<Comparative Example 2>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-4, respectively, and compound (2-1) as a material for a light emitting auxiliary layer was replaced with compound (EAL-1). An organic EL device was obtained in the same manner as in Example 12. ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 460 nm and CIE chromaticity (x, y) = (0.139, 0.143) was obtained. In addition, the driving voltage was 3.78V, and the external quantum efficiency was 7.54%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 301 hours.

<Example 18>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-7, respectively. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 454 nm and CIE chromaticity (x, y) = (0.142, 0.101) was obtained. In addition, the driving voltage was 4.95V, and the external quantum efficiency was 5.22%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 258 hours.

<Example 19>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-8, respectively. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.144, 0.157) was obtained. In addition, the driving voltage was 4.64V, and the external quantum efficiency was 6.34%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 439 hours.

<Comparative Example 3>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

BH-1 as a host material and BD-1 as a dopant material were replaced with BH-5 and BD-8, respectively, and compound (2-1) as a material for a light emitting auxiliary layer was replaced with compound (EAL-1). An organic EL device was obtained in the same manner as in Example 12. ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 455 nm and CIE chromaticity (x, y) = (0.147, 0.158) was obtained. In addition, the driving voltage was 3.59V, and the external quantum efficiency was 6.61%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 174 hours.

<Example 20>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-4 and BD-6, respectively. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 460 nm and CIE chromaticity (x, y) = (0.135, 0.115) was obtained. In addition, the driving voltage was 4.47V, and the external quantum efficiency was 7.19%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 180 hours.

<Comparative Example 4>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

BH-1 as a host material and BD-1 as a dopant material were replaced with BH-4 and BD-6, respectively, and compound (2-1) as a material for a light-emitting auxiliary layer was replaced with compound (EAL-1). An organic EL device was obtained in the same manner as in Example 12. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 460 nm and CIE chromaticity (x, y) = (0.135, 0.118) was obtained. In addition, the driving voltage was 3.60V, and the external quantum efficiency was 7.39%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 94 hours.

<Example 21>

<Device using compound (2-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12, except that BH-1 as a host material and BD-1 as a dopant material were replaced with BH-4 and BD-5, respectively. ^{As a result of measuring the characteristics at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 461 nm and CIE chromaticity (x, y) = (0.135, 0.125) was obtained. In addition, the driving voltage was 4.44V, and the external quantum efficiency was 7.07%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 350 hours.

<Comparative Example 5>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

BH-1 as a host material and BD-1 as a dopant material were replaced with BH-4 and BD-5, respectively, and compound (2-1) as a material for a light emitting auxiliary layer was replaced with compound (EAL-1). An organic EL device was obtained in the same manner as in Example 12. ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 462 nm and CIE chromaticity (x, y) = (0.134, 0.128) was obtained. In addition, the driving voltage was 3.58V, and the external quantum efficiency was 7.58%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 109 hours.

<Example 22>

<Device using compound (2-62) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that compound (2-1) as a material for the light-emitting auxiliary layer was replaced with compound (2-62). ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 457 nm and CIE chromaticity (x, y) = (0.139, 0.126) was obtained. In addition, the driving voltage was 5.63V and the external quantum efficiency was 6.29%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 360 hours.

<Example 23>

<Device using compound (2-21) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-21). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.117) was obtained. In addition, the driving voltage was 4.77V, and the external quantum efficiency was 6.96%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 396 hours.

<Example 24>

<Device using compound (2-41) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-41). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 459 nm and CIE chromaticity (x, y) = (0.137, 0.135) was obtained. In addition, the driving voltage was 5.38V and the external quantum efficiency was 5.84%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 600 hours.

<Example 25>

<Device using compound (2-1) as a light emitting auxiliary layer>

In the same manner as in Example 1, an organic electroluminescent device was obtained. Using the ITO electrode as the anode and the Al electrode as the cathode, applying a DC voltage to ^{measure the characteristics at 1000cd/m 2} light emission. As a result, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.120) was was obtained In addition, the driving voltage was 4.90V, and the external quantum efficiency was 5.61%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 400 hours.

<Example 26>

<Device using compound (2-3) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-3). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 5.17V and the external quantum efficiency was 5.55%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 407 hours.

<Example 27>

<Device using compound (2-5) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (2-5). ^{As a result of measuring the characteristics at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.120) was obtained. In addition, the driving voltage was 5.08V, and the external quantum efficiency was 5.00%. In addition, the time for maintaining the luminance of 80% or more of the initial luminance was 530 hours.

<Comparative Example 6>

<Device using compound (EAL-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (EAL-1). ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.143, 0.121) was obtained. In addition, the driving voltage was 3.72V, and the external quantum efficiency was 6.99%. In addition, the time for maintaining the luminance of 90% (900cd/m ^{2 ) or more of the initial luminance was 65 hours.}

<Example 28>

<A device using compound (3-5) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (3-5). ^{As a result of measuring the characteristics at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 457 nm and CIE chromaticity (x, y) = (0.139, 0.124) was obtained. In addition, the driving voltage was 5.32V and the external quantum efficiency was 6.63%. In addition, the time for maintaining the luminance of 90% or more of the initial luminance was 228 hours.

<Example 29>

<Device using compound (3-8) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that compound (2-1) as a material for the light-emitting auxiliary layer was replaced with compound (3-8). ^{As a result of measuring the characteristic at the time of 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.121) was obtained. In addition, the driving voltage was 7.50V, and the external quantum efficiency was 5.00%. In addition, the time for maintaining the luminance of 90% or more of the initial luminance was 258 hours.

<Example 30>

<Device using compound (1-1) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12 except that the compound (2-1) as a material for the light-emitting auxiliary layer was replaced with the compound (1-1). ^{As a result of measuring the characteristics at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 457 nm and CIE chromaticity (x, y) = (0.139, 0.127) was obtained. In addition, the driving voltage was 5.89V and the external quantum efficiency was 6.29%. In addition, the time for maintaining the luminance of 90% or more of the initial luminance was 331 hours.

<Example 31>

<Device using compound (2-87) as a light emitting auxiliary layer>

An organic EL device was obtained in the same manner as in Example 12, except that compound (2-1) as a material for a light emitting auxiliary layer was replaced with compound (2-87), and ETL-1 as a material for an electron transport layer was changed to ETL-4. . ^{As a result of measuring the characteristic at 1000 cd/m 2} light emission by applying a DC voltage, blue light emission with a wavelength of 456 nm and CIE chromaticity (x, y) = (0.140, 0.123) was obtained. In addition, the driving voltage was 4.64V, and the external quantum efficiency was 6.28%. In addition, the time for maintaining the luminance of 90% or more of the initial luminance was 131 hours.

[Industrial Applicability]

According to a preferred aspect of the present invention, it is possible to efficiently utilize the TTF phenomenon occurring in the light emitting layer and to provide an organic EL device having improved external quantum efficiency, a display device having the same, and a lighting device having the same.

[Explanation of code]

100 organic EL device

101 board

102 anode

103 hole injection layer

104 hole transport layer

105 light emitting layer

106 electron transport layer

107 electron injection layer

108 cathode

110 Light-emitting auxiliary layer

Claims (18)

A material for a light-emitting auxiliary layer, which is used for a light-emitting auxiliary layer between the light-emitting layer and the electron-transporting layer in an organic electroluminescent device, and containing a benzofluorene compound represented by the following general formula (2) or (3),
_{A material for a} light emitting auxiliary layer having a triplet energy E ^{T a larger than the triplet energy E T} _h of the host material in the light emitting layer.

(In the above formulas (2) and (3),
R ¹ and R ² are optionally substituted C6-C20 aryl,
R ³ and R ⁴ each independently represent optionally substituted alkyl having 1 to 6 carbon atoms or optionally substituted aryl having 6 to 12 carbon atoms, and when R ³ and R ⁴ are aryl, aryls are bonded to each other to form a ring may form, and
The substituents for R ¹ , R ² , R ³ and R ⁴ are each independently methyl, ethyl, propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl. ) delete delete delete delete delete According to claim 1,
R ¹ and R ² are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl or phenanthryl, and
R ³ and R ⁴ are each independently methyl, ethyl, propyl, t-butyl, phenyl or biphenylyl, and phenyl or biphenylyl may be bonded to each other to form a ring;
A material for a light emitting auxiliary layer. It is used for the light emission auxiliary layer between the light emitting layer and the electron transport layer in the organic electroluminescent device, and the following formulas (2-1), (2-2), (2-3), (2-4), Formula (2-5), Formula (2-21), Formula (2-41), Formula (2-61), Formula (2-62), Formula (2-85), Formula (2-87), Formula A material for a light emitting auxiliary layer comprising a benzofluorene compound represented by any one of (3-5), formula (3-6) and formula (3-8),
_{A material for a} light emitting auxiliary layer having a triplet energy E ^{T a larger than the triplet energy E T} _h of the host material in the light emitting layer.

delete A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport layer disposed between the cathode and the light emitting layer, and a light emitting auxiliary layer disposed between the light emitting layer and the electron transport layer. , as an organic electroluminescent device,
The light emitting auxiliary layer is formed of the light emitting auxiliary layer material according to claim 1, an organic electroluminescent device. 11. The method of claim 10,
The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,
The triplet energy E ^T _h of the host material is smaller than the ^{triplet energy E T} _{a of the} material for the light emitting auxiliary layer,
organic electroluminescent device. 11. The method of claim 10,
The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,
The triplet energy E ^T _d of the dopant material is greater than the ^{triplet energy E T} _h of the host material,
organic electroluminescent device. 11. The method of claim 10,
The light emitting layer is made of a host material and a dopant material having a fluorescence emission having a peak at an emission wavelength of 400 to 500 nm,
The host material contains at least one selected from the group consisting of anthracene derivatives and pyrene derivatives,
The dopant material contains at least one selected from the group consisting of an amine-containing benzofluorene derivative, an amine-containing pyrene derivative, an amine-free pyrene derivative, an amine-containing chrysene derivative, and an amine-containing styryl derivative.
organic electroluminescent device. 11. The method of claim 10,
The material for the electron transport layer contains a heterocyclic compound, an organic electroluminescent device. 15. The method of claim 14,
The heterocyclic compound is at least one selected from the group consisting of pyridine derivatives, thiazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, phenanthroline derivatives and phosphine oxide derivatives, an organic electroluminescent device. 11. The method of claim 10,
The Bahia relationship Community A _e of the material for the electron transport layer to form a community Bahia A _a and the electron transport layer of the light-emitting auxiliary material, A _a> A _e of -0.8eV,
organic electroluminescent device. A display device provided with the organic electroluminescent device according to any one of claims 10 to 16. A lighting device provided with the organic electroluminescent device according to any one of claims 10 to 16.

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