TW201418247A - Organic electroluminescent element - Google Patents

Abstract

This organic electroluminescent element comprises a negative electrode, a positive electrode, and one or more organic layers that are arranged between the negative electrode and the positive electrode and include at least a light emitting layer. This organic electroluminescent element is characterized in that the light emitting layer contains an anthracene derivative represented by general formula (1), and a chrysene derivative represented by general formula (21) or a substance represented by general formula (41).

Description

Organic electroluminescent element

The present invention relates to an organic electroluminescent element.

An organic electroluminescence device (hereinafter sometimes simply referred to as an organic EL device) using an organic substance may be used as a solid-state light-emitting type large-area full-color display element, and has been developed in various ways. A general EL element is composed of a light-emitting layer and a counter electrode sandwiching one of the light-emitting layers. When an electric field is applied between the electrodes, electrons are injected from the cathode side, and holes are injected from the anode side. This electron recombines with the hole in the light-emitting layer to generate an excited state, and when returned from the excited state to the substrate state, the energy is released in the form of light.

In the conventional organic EL device, the driving voltage is higher than that of the inorganic light-emitting diode, and the light-emitting luminance or the light-emitting efficiency is also low. Moreover, the characteristics are deteriorated significantly and cannot be put to practical use. Recently, organic EL elements have been gradually improved, but further high luminous efficiency, long life, color reproducibility, and the like are required.

The performance of the organic EL element has been gradually improved by the improvement of the luminescent material for organic EL. In particular, the color purity of the blue organic EL element is increased (short wavelength of the emission wavelength) to improve the color reproducibility of the display. Important technology.

An example of a material used for the light-emitting layer, for example, Document 1 (International Publication No. 2010/137285) discloses an anthracene derivative having dibenzofuran as a substituent. In Document 1, it is described that an organic EL element used as a host material of the derivative is driven at a low voltage and exhibits blue light emission of a short wavelength.

However, the organic EL device described in Document 1 is still insufficient in efficiency and lifetime, and when the organic EL device is used for a light source of an electronic device such as an illumination device or a display device, it is necessary to further improve efficiency and longer life.

Summary of invention

An object of the present invention is to provide an organic electroluminescence element which is driven at a low voltage and emits light with high efficiency and long life.

[1] An organic electroluminescence device according to an embodiment of the present invention, comprising: a cathode; an anode; and an organic layer disposed between the cathode and the anode and containing at least one or more of the light-emitting layers; It is an anthracene derivative represented by the following general formula (1) and represented by the following general formula (21) derivative.

[In the above general formula (1), any of R ¹ ~ R ¹⁰ c departments for bonded to L ¹ is a single bond, is not used to L ¹ bonded to R ¹ ~ R ¹⁰ are each selected from a hydrogen atom , halogen atom, hydroxyl group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted The aryloxy group having 6 to 30 carbon atoms forming a ring, the substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, the substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, Or a substituted or unsubstituted heterocyclic group having 5 to 30 atomic number of the ring forming ring, and L ¹ is selected from any one of a single bond or a linking group, and the number of carbon atoms forming the ring in which the above linking group is substituted or unsubstituted 6 to 30 (a+1) of an aromatic hydrocarbon group, a substituted or unsubstituted ring-forming atomic group having 5 to 30 (a+1)-valent heterocyclic group, or the aforementioned substituted or unsubstituted ring forming ring An aromatic hydrocarbon group having 6 to 30 carbon atoms and a (a+1)-valent group formed by a bond of 2 to 4 groups selected from the above-mentioned substituted or unsubstituted heterocyclic group having 5 to 30 atomic number of the ring-forming ring.

a, b, and c each represent an integer of 1 to 4.

Z ¹ is represented by the following general formula (2). ]

[In the above general formula (2), X ¹ is selected from any of an oxygen atom or a sulfur atom.

R ¹¹¹ to R ¹¹⁸ are each synonymous with R ¹ to R ¹⁰ which are not used for bonding with L ^{1 in the} above general formula (1).

However, two substituents adjacent to at least one of R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹¹⁷ or R ¹¹⁷ and R ¹¹⁸ are mutually The bond forms a ring represented by the following general formula (3) or (4). ]

[In the above general formula (3), y ¹ and y ² represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2).

In the above general formula (4), y ³ and y ⁴ represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2).

R ¹²¹ to R ¹²⁴ and R ¹²⁵ to R ¹²⁸ are each synonymous with R ¹ to R ¹⁰ which are not used for bonding with L ^{1 in the} above general formula (1).

X ² is selected from any of an oxygen atom or a sulfur atom.

In the above general formula (2), R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²¹ to R ¹²⁴ of the above general formula (3) or R ¹¹¹ to R which do not form a ring in the above general formula (2) ¹¹⁸ and any one of R ¹²⁵ to R ¹²⁸ of the above general formula (4) are a single bond for bonding to L ^{1 of the} above general formula (1). ]

[In the above general formula (21), R ²⁰ to R ²⁹ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted meyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring.

Ar ²¹ to Ar ²⁴ each represent a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.

When Ar ²¹ to Ar ²⁴ have an alkyl group as a substituent, each has at least two or more alkyl groups].

[2] An organic electroluminescence device according to another embodiment of the present invention, comprising: a cathode; an anode; an organic layer disposed between the cathode and the anode and containing at least one or more of the light-emitting layers; and the light-emitting layer It is an anthracene derivative represented by the above general formula (1) and an anthracene derivative represented by the following general formula (41).

[In the above general formula (41), R ²¹ to R ²⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted methyroalkyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and Ar ²¹ to Ar ²⁴ each represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, or a substituted or a A heterocyclic group substituted with 5 to 30 atoms forming a ring.

In the above general formula (41), at least one of Ar ²¹ to Ar ²⁴ is a heterocyclic group represented by the following formula (42). ]

[In the above general formula (42), R ²¹¹ to R ²¹⁷ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20; Alkenyl, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted metaalkyl group, substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms or substituted or unsubstituted ring forming ring A heterocyclic group having 5 to 30 atoms.

Further, R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁶ and R ²¹⁷ are bonded to each other to form a saturated or unsaturated ring, and the rings may be Replace.

X ²¹ is selected from any of an oxygen atom or a sulfur atom.

Y ²¹ is a single bond bonded to the nitrogen atom of the above general formula (41)].

[3] The organic electroluminescence device of the present invention, wherein Z ¹ in the above general formula (1) is preferably represented by any one of the following general formulas (5) to (7).

[In the above general formulas (5) to (7), R ¹³¹ to R ¹⁴⁰ , R ¹⁴¹ to R ¹⁵⁰ , and R ¹⁵¹ to R ¹⁶⁰ are each not in the above general formula (1), and are not used for bonding to L ¹ . ¹ ~ R ^{10 is} synonymous.

However, any one of R ¹³¹ to R ¹⁴⁰ , any of R ¹⁴¹ to R ¹⁵⁰ , and any of R ¹⁵¹ to R ¹⁶⁰ are used for bonding with L ¹ , and the group for bonding with L ¹ is a single bond. .

X ^1, X ² are each the aforementioned general formula X ¹ (2) in the foregoing in the general formula (4) X ² are synonymous. X ¹ and X ² are the same or different].

[4] The organic electroluminescence device of the present invention, wherein Z ¹ in the above general formula (1) is preferably represented by any one of the following general formulas (8) to (10).

[In the above general formulas (8) to (10), R ¹⁶¹ to R ¹⁷⁰ , R ¹⁷¹ to R ¹⁸⁰ , and R ¹⁸¹ to R ¹⁹⁰ each are the same as those in the above general formula (1), which are not used for bonding with L ¹ . ¹ ~ R ^{10 is} synonymous.

However, any of R ¹⁶¹ to R ¹⁷⁰ , any of R ¹⁷¹ to R ¹⁸⁰ , and any of R ¹⁸¹ to R ¹⁹⁰ are used for bonding with L ¹ , and the group for bonding with L ¹ is a single bond. .

The X ¹ system is synonymous with X ¹ in the above general formula (2)].

[5] The above organic electroluminescence device of the present invention, wherein b of the above general formula (1) is preferably 1.

[6] The above organic electroluminescence device of the present invention, wherein a of the above general formula (1) is preferably 1 or 2.

[7] The organic electroluminescence device of the present invention, wherein at least one of R ⁹ and R ¹⁰ of the above general formula (1) is preferably a single bond for bonding with L ¹ .

[8] The above organic electroluminescence device of the present invention, wherein R ^{9 of the} above general formula (1) is preferably an aromatic hydrocarbon group selected from a substituted or unsubstituted ring-forming carbon number of 6 to 30, or substituted or absent. A group substituted with a heterocyclic group having 5 to 30 atoms in the ring.

[9] The above organic electroluminescence device of the invention, wherein X ¹ and X ^{2 are} preferably an oxygen atom.

[10] The organic electroluminescence device of the present invention, wherein any one of R ¹⁶¹ to R ¹⁶⁴ , any of R ¹⁷¹ to R ¹⁷⁴ , and R ¹⁸¹ to R ^{184 in} the above general formulas (8) to (10) Any one for bonding to L ¹ and a group for bonding to L ¹ is preferably a single bond.

[11] The organic electroluminescence device of the present invention, wherein the anthracene derivative represented by the above general formula (1) is preferably represented by any one of the following general formulas (15) to (20).

[R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (15) to (20) are each synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (15) to (20) is synonymous with X ¹ in the above general formula (2)].

[12] The organic electroluminescence device of the present invention, wherein the anthracene derivative represented by the above general formula (1) is preferably represented by any one of the following general formulas (51) to (56).

[R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (51) to (56) are synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (51) to (56) is synonymous with X ¹ in the above general formula (2)].

[13] The organic electroluminescence device of the present invention, wherein the anthracene derivative represented by the above formula (1) is preferably represented by any one of the following general formulas (57) to (62).

[R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (57) to (62) are synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (57) to (62) is synonymous with X ¹ in the above general formula (2)].

[14] The organic electroluminescence device of the present invention, wherein R ²⁰ to R ^{29 of the} above general formula (21) are preferably a hydrogen atom.

[15] The organic electroluminescence device of the present invention, wherein Ar ²¹ and Ar ²³ of the above general formula (41) are preferably a heterocyclic group represented by the above general formula (42).

[16] The organic electroluminescence device of the present invention, wherein R ²¹ to R ^{28 of the} above general formula (41) are preferably a hydrogen atom.

[17] The above organic electroluminescent device of the present invention, wherein R ²² and R ^{26 of the} above general formula (41) are preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon. The alkylmercaptoalkyl group having 3 to 30 atoms, and R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ^{28 in the} above general formula (41) are a hydrogen atom.

[18] The above organic electroluminescence device of the present invention, wherein X ^{21 of the} above general formula (42) is preferably an oxygen atom.

1‧‧‧ cathode

2‧‧‧Electronic transport layer

3‧‧‧Lighting layer

4‧‧‧ hole transport layer

5‧‧‧Anode

6‧‧‧Substrate

Fig. 1 is a schematic configuration diagram showing an example of an organic electroluminescence device according to an embodiment of the present invention.

<First embodiment> (Elements of organic EL elements)

The element configuration of the organic EL device according to an embodiment of the present invention will be described below.

The organic EL device of the present embodiment includes an organic layer between a pair of electrodes. The organic layer has at least one layer of an organic compound. The organic layer may also contain an inorganic compound.

In the organic EL device of the present embodiment, at least one of the organic layers has a light-emitting layer. Therefore, the organic layer may be composed of, for example, a light-emitting layer, or may have a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport. A layer used for a known organic EL element such as a layer, a hole barrier layer, or an electron barrier layer.

The component composition of the organic EL element, for example,

(a) anode / luminescent layer / cathode

(b) Anode/hole injection ‧ Transport layer / luminescent layer / cathode

(c) Anode / luminescent layer / electron injection ‧ transport layer / cathode

(d) Anode/hole injection ‧ Transport layer / luminescent layer / Electron injection ‧ Transport layer / Cathode

(e) Anode/hole injection ‧ transport layer / luminescent layer / barrier layer / electron injection ‧ transport layer / cathode, etc.

Among the above, the configuration of (d) is preferably used, but it is of course not limited thereto.

In addition, the above-mentioned "light-emitting layer" means an organic layer having a light-emitting function, and when a doping system is employed, a host material and a dopant material are included. At this time, the host material mainly promotes recombination of electrons and holes, and has a function of enclosing excitons in the light-emitting layer, and the dopant material has a function of efficiently emitting excitons obtained by recombination. In the case of a phosphorescent element, the host material mainly has a function of enclosing excitons generated by the dopant in the light-emitting layer.

The above-mentioned "hole injection ‧ transport layer" means "at least one of the hole injection layer and the hole transport layer", and "electron injection ‧ transport layer" means "at least one of the electron injection layer and the electron transport layer" One." Here, when the hole injection layer and the hole transport layer are provided, it is preferable to provide a hole injection layer on the anode side. Moreover, when the electron injecting layer and the electron transporting layer are provided, the cathode side is provided It is preferable to place an electron injecting layer.

In the present embodiment, the electron transporting layer means an organic layer having the highest electron mobility among the organic layers existing in the electron transporting region between the light emitting layer and the cathode. When the electron transporting region is composed of a single layer, the layer is an electron transporting layer. Further, in the phosphorescent organic EL device, as shown in the configuration (e), in order to prevent the diffusion of the excitation energy generated by the light-emitting layer, the electron mobility may not necessarily be between the light-emitting layer and the electron transport layer. The high barrier layer and the organic layer adjacent to the light-emitting layer do not necessarily correspond to the electron transport layer.

Fig. 1 is a view showing a schematic configuration of an example of an organic EL device in the present embodiment.

The organic EL element 1 is a light-transmitting substrate 2, an anode 3, a cathode 4, and an organic layer 10 disposed between the anode 3 and the cathode 4.

The organic layer 10 has a light-emitting layer 5 containing a host material and a dopant material. Further, the organic layer 10 is provided between the light-emitting layer 5 and the anode 3, and has a hole transport layer 6. Further, the organic layer 10 has an electron transport layer 7 between the light-emitting layer 5 and the cathode 4.

(lighting layer)

In the organic EL device of the present embodiment, the luminescent layer contains an anthracene derivative represented by the following general formula (1) and is represented by the following general formula (21). derivative.

. Body material

In the organic EL device of the present embodiment, an anthracene derivative represented by the following general formula (1) can be used as a host material.

The foregoing general formula (1), any one of R ¹ ~ R ¹⁰ c departments for a single bond and L ¹ bond to the junction, the junction is not ^used, R ¹ and L key ¹ ~ R ¹⁰ are each selected from a hydrogen atom, Halogen atom, hydroxyl group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted An aryloxy group having 6 to 30 carbon atoms in the ring, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, or Any one of substituted or unsubstituted heterocyclic groups of 5 to 30 atoms forming a ring.

L ¹ is selected from any one of a single bond or a linking group, and the above-mentioned linking group is substituted or unsubstituted to form a ring having a carbon number of 6 to 30 (a+1) of an aromatic hydrocarbon group, a substituted or unsubstituted ring. a heterocyclic group having an atomic number of 5 to 30 (a+1) or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituted or unsubstituted atomic number of the ring 5 The group selected from the heterocyclic group of ~30 is 2 to 4 bonded groups to form (a+1) valence groups.

a, b, and c each represent an integer of 1 to 4.

Z ¹ is represented by the following general formula (2).

[In the above general formula (2), X ¹ is selected from any of an oxygen atom or a sulfur atom.

R ¹¹¹ to R ¹¹⁸ are each synonymous with R ¹ to R ¹⁰ which are not used for bonding with L ^{1 in the} above general formula (1).

However, two substituents adjacent to at least one of R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹¹⁷ or R ¹¹⁷ and R ¹¹⁸ are mutually The bond forms a ring represented by the following general formula (3) or (4).

In the above general formula (3), y ¹ and y ² represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2).

In the above general formula (4), y ³ and y ⁴ represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2).

R ¹²¹ to R ¹²⁴ and R ¹²⁵ to R ¹²⁸ are each synonymous with R ¹ to R ¹⁰ which are not used for bonding with L ^{1 in the} above general formula (1).

X ² is selected from any of an oxygen atom or a sulfur atom.

In the above general formula (2), R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²¹ to R ¹²⁴ of the above general formula (3) or R ¹¹¹ to R which do not form a ring in the above general formula (2) ¹¹⁸ and any one of R ¹²⁵ to R ¹²⁸ of the above general formula (4) are a single bond for bonding to L ^{1 of the} above general formula (1).

Further, in the above general formula (1), Z ^{1 is} preferably one of the following general formulas (5) to (7). For example, the following general formula (5) is that the y ³ of the above general formula (4) corresponds to the position of the carbon atom bonded by R ¹¹⁴ in the above general formula (2), and y ⁴ corresponds to the above general formula (2). The position of the carbon atom to which R ¹¹³ is bonded.

~ In ^{(7), R 131 ~ R} 140, R 141 ~ R 150, R 151 ~ R L 1 bonded to ^one of R & lt foregoing general formula (5) above, respectively ¹⁶⁰ general formula (1) is not used and ~R ^{10 is} synonymous.

However, any one of R ¹³¹ to R ¹⁴⁰ , any of R ¹⁴¹ to R ¹⁵⁰ , and any of R ¹⁵¹ to R ¹⁶⁰ are used for bonding with L ¹ , and the group for bonding with L ¹ is a single bond. .

X ^1, X ² are each the aforementioned general formula X ¹ (2) in the foregoing in the general formula (4) X ² are synonymous. X ¹ and X ² are the same or different.

Further, in the above general formula (1), Z ^{1 is} preferably represented by any one of the following general formulas (8) to (10).

In ^{~ (10), R 161 ~} R 170, R 171 ~ R 180, R 181 ~ R L 1 bonded to ^one of R & lt foregoing general formula (8) above, respectively ¹⁹⁰ general formula (1) is not used and ~R ^{10 is} synonymous.

However, any of R ¹⁶¹ to R ¹⁷⁰ , any of R ¹⁷¹ to R ¹⁸⁰ , and any of R ¹⁸¹ to R ¹⁹⁰ are used for bonding with L ¹ , and the group for bonding with L ¹ is a single bond. .

The X ¹ system is synonymous with X ¹ in the above general formula (2).

Z ¹ in the above general formula (1) is particularly preferably represented by any one of the above general formulas (8) to (10).

In the above general formula (1), b is preferably 1, a is preferably 1 or 2, and a is more preferably 1.

At least one of R ⁹ and R ¹⁰ of the above general formula (1) is preferably a single bond for bonding to L ¹ .

Further, R ^{9 of the} above general formula (1) is preferably an aromatic hydrocarbon group selected from a substituted or unsubstituted ring-forming carbon number of 6 to 30, or a substituted or unsubstituted ring-forming atomic number of 5 to 30. The group of the ring group is more preferably represented by the following general formula (11).

In the above general formula (11), Ar ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms selected from a substituted or unsubstituted ring, or a substituted or unsubstituted heterocyclic group having 5 to 30 atoms forming a ring. Group.

Each of Ra is synonymous with R ¹ to R ¹⁰ which is not used for bonding with L ^{1 in the} above general formula (1).

d represents an integer from 1 to 4.

When d is 2 to 4, the complex Ra is the same or different.

When R ⁹ of the above general formula (1) is a group selected from such a group, R ^{10 of the} above general formula (1) is more preferably a single bond for bonding with L ¹ .

Further, R ^{9 of the} above general formula (1) is preferably a substituted or unsubstituted condensed aromatic hydrocarbon group having 10 to 30 carbon atoms forming a ring.

In the above general formula (1), X ¹ and X ^{2 are} preferably an oxygen atom.

In the above general formulas (8) to (10), any one of R ¹⁶¹ to R ¹⁶⁴ , any of R ¹⁷¹ to R ¹⁷⁴ , and any of R ¹⁸¹ to R ¹⁸⁴ are used for bonding with L ¹ and used for The group bonded to L ¹ is preferably a single bond.

The anthracene derivative represented by the above general formula (1) is preferably represented by any one of the following general formulas (15) to (20).

R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (15) to (20) are each synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (15) to (20) is synonymous with X ¹ in the above general formula (2).

The anthracene derivative represented by the general formula (1) is preferably represented by any one of the following general formulas (51) to (56).

The R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (51) to (56) are synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (51) to (56) is synonymous with X ¹ in the above general formula (2).

The anthracene derivative represented by the above general formula (1) is preferably as follows. Any one of the formulas (57) to (62).

R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (57) to (62) are synonymous with R ¹ to R ⁸ in the above general formula (1).

The X ¹ in the above general formulas (57) to (62) is synonymous with X ¹ in the above general formula (2).

The anthracene derivative represented by any one of the above general formulas (57) to (62) corresponds to a case where L ¹ in the above general formulas (15) to (20) is a stretching phenyl group. In the above general formulas (57) to (62), for the carbon atom of the 6-membered ring of the phenylene group, the anthracene ring is bonded to the aforementioned condensed ring having X ¹ .

In the above general formulas (13) to (20) and (51) to (62), X _{1 is} preferably an oxygen atom.

Next, each substituent described in the above general formulas (1) to (20) and (51) to (62) will be described.

Specific examples of the substituents described in the above general formulae (1) to (20) and (51) to (62) include, for example, a halogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted amino group, and a substituted or unsubstituted one. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted linear, branched or cyclic haloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted linear, branched or cyclic haloalkoxy group having 1 to 20 carbon atoms, substituted Or an unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted ring, and a carbon number of 6 to 30 A hydrocarbon group, a substituted or unsubstituted heterocyclic group having 5 to 30 atomic atoms forming a ring.

The halogen atoms in the above general formulas (1) to (20) and (51) to (62) are, for example, fluorine, chlorine, bromine, iodine or the like, preferably fluorine.

The substituted or unsubstituted amino group in the above general formulae (1) to (20), (51) to (62), for example, an amine group substituted with an aromatic hydrocarbon group, preferably a phenylamine group. The aromatic hydrocarbon group of the substituted amino group may, for example, be an aromatic hydrocarbon group having 6 to 30 carbon atoms which forms a ring.

The alkyl group having 1 to 20 carbon atoms in the above general formulas (1) to (20), (51) to (62) may be any of linear, branched or cyclic, linear or branched alkyl groups. Base, for example, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, N-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodecyl, n-tridedecyl, n-tetradecyl, n-pentadecayl, n-hexadeca , n-heptadecyl, n-octadecyl, neopenta , 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl, hydroxymethyl, 1-hydroxyl Ethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxy-t-butyl, 1,2 , 3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-Dichloro-t-butyl, 1,2,3-trichloropropyl, bromomethyl, 1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2- Dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-t-butyl, 1,2,3-tribromopropyl, iodomethyl, 1-iodoethyl, 2- Iodine ethyl, 2-iodoisobutyl, 1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-t-butyl, 1,2,3-triiodide Propyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl , 2,3-Diamino-t-butyl, 1,2,3-triaminopropyl, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoiso Butyl, 1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2,3-dicyano-t-butyl 1,2,3-Tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 1,2-dinitroethyl, 2,3-dinitro-t -butyl, 1,2,3-trinitropropyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propane Base and so on.

A cyclic alkyl group (cycloalkyl group), for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 4-methylcyclohexyl, 3,5-tetramethylcyclohexyl, 1 - adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. Among them, preferably A Base, isopropyl, t-butyl, cyclohexyl.

The linear, branched or cyclic haloalkyl group having 1 to 20 carbon atoms, for example, the alkyl group having 1 to 20 carbon atoms is substituted by one or more halogen atoms. Specific examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, and a trifluoromethylmethyl group.

The linear, branched or cyclic alkoxy group having ¹ to 20 carbon atoms in the above general formulae (1) to (20) and (51) to (62) is represented by -OY ¹ . An example of the Y ¹ is an alkyl group having 1 to 20 carbon atoms. The alkoxy group is, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group.

Among the above alkoxy groups, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 8 carbon atoms is more preferred. Particularly preferred is an alkoxy group having 1 to 4 carbon atoms.

The linear, branched or cyclic haloalkoxy group having 1 to 20 carbon atoms in the above general formulas (1) to (20) and (51) to (62), for example, the above carbon number 1 to 20 The alkoxy group is substituted by a halogen group of 1 or more.

The aryloxy group having 6 to 30 carbon atoms forming a ring in the above general formulae (1) to (20) and (51) to (62) is represented by -OZ ² . Examples of the Z ² include the following aromatic hydrocarbon groups having 6 to 30 carbon atoms forming a ring. This aryloxy group is, for example, a phenoxy group.

The arylthio group having 6 to 30 carbon atoms forming a ring in the above general formulas (1) to (20) and (51) to (62) is represented by -SZ ³ . Examples of the Z ³ include the following aromatic hydrocarbon groups having 6 to 30 carbon atoms forming a ring.

The aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring in the above general formulae (1) to (20) and (51) to (62), for example, a non-condensed aromatic hydrocarbon group and a condensed aromatic hydrocarbon group, more specifically For example, there are phenyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, tetraphenyl, fluoranthenyl, fluorenyl (pyrenyl), triphenylenyl, phenanthrenyl, fluorenyl, 9,9-dimethylindenyl, benzo[c]phenanthryl, benzo[a] Phenyl, naphtho[1,2-c]phenanthryl, naphtho[1,2-a]triphenylene, dibenzo[a,c]linked triphenyl, benzo[b]fluorene Among the above aromatic hydrocarbon groups, the aromatic hydrocarbon group having 6 to 20 carbon atoms in the ring is more preferably formed, and particularly preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms in the ring. Further, a phenyl group, a naphthyl group, a terphenyl group, a fluoranthene group, a 9,9-dimethylindenyl group, a benzo[c]phenanthrenyl group or a phenanthryl group is preferred.

The aromatic heterocyclic group having 5 to 30 atoms in the ring form in the above general formulae (1) to (20) and (51) to (62), for example, a non-condensed aromatic heterocyclic ring and a condensed aromatic heterocyclic ring, More specifically, for example, pyrrolyl, pyrazinyl, pyridyl, decyl, isodecyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophene , quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthryl, anthranyl, phenanthroline, thienyl and by pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, triazine ring, anthracene ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, indazole ring, furan ring, thiophene ring , oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyran ring, dibenzofuran ring a group formed by a benzo[c]dibenzofuran ring. Among the above heterocyclic groups, a heterocyclic group having 5 to 20 atoms in the ring is more preferable, and a heterocyclic group having 5 to 12 atoms in the ring is particularly preferable. And, preferably dibenzofuran ring, a dibenzofuran group (furanyl) ring, a carbazole ring.

In the above general formula (1), R ¹ to R ¹⁰ which are not bonded to L ¹ are used, and a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable.

When R ⁹ is a condensed aromatic hydrocarbon group having 10 to 30 carbon atoms forming a ring, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 9-fluorenyl group, and 1-phenanthryl group are preferred. , 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-thyltetraphenyl (naphthacenyl), 2-fused tetraphenyl, 9-fused tetraphenyl, 1-indenyl, 2-indenyl, 4-indenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl and 4-methyl-1-indenyl.

In the above general formula (1), when L ¹ is a linking group, for example, a (a+1)-valent aromatic hydrocarbon group having a carbon number of 6 to 30 which is substituted or unsubstituted is formed, and a substituted or unsubstituted ring is formed. a heterocyclic group having an atomic number of 5 to 10 (a+1), or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituted or unsubstituted atomic number of 5 to 10 The selected group of the heterocyclic group is a (a+1)-valent group formed by 2 to 4 bonding.

Specific examples of the aromatic hydrocarbon group having a (a+1)-valent carbon number of 6 to 30 carbon atoms forming the ring include, for example, those having an aromatic hydrocarbon group having 6 to 30 carbon atoms forming the ring, and forming (a+1) valence. The group of people.

Further, a specific example of the heterocyclic group having a (a+1)-valent atomic number of 5 to 30 atoms in the ring is, for example, a heterocyclic group having 5 to 30 atomic number of the ring formed, and (a+1) is formed. The base of the price.

When L ¹ is an aromatic hydrocarbon group having a (a+1)-valent carbon number of 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a naphthyl group or a 9,9-dimethyl fluorene group. base.

When L ¹ is a (he+1)-valent heterocyclic group having a ring number of atoms of 6 to 30, more preferably a heterocyclic group, for example, a pyridyl group, a pyrimidinyl group, a dibenzofuranyl group or an oxazolyl group.

L ^{1 is a group selected} from a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 10 atoms forming a ring, in the range of 2 to 4 When the (a+1)-valent group formed by bonding is bonded, the aromatic hydrocarbon group and the heterocyclic group are each, for example, as described above. The aromatic hydrocarbon group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted fluorenyl group, a substituted group. Or an unsubstituted fluorenyl group, preferably a heterocyclic group selected from substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted Or an unsubstituted triazinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group. The (a+1) price is preferably 2.

More preferably, it is a structure of the following structure or (a+1) valence derived from the following structure.

L ^{1 is a group selected} from a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 10 atoms forming a ring, in the range of 2 to 4 Preferred structures of the anthracene derivative formed by the bonding are, for example, the following.

R ¹¹¹ to R ¹¹⁴ in the above general formula (2) are more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

R ¹²¹ to R ¹²⁴ and R ¹²⁵ to R ¹²⁸ in the above general formulas (3) and (4) are more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In the above general formula (2), when the substituent of R ¹¹¹ and R ¹¹² is a ring represented by the above general formula (4), R ¹¹⁷ and R ^{118 are} preferably a hydrogen atom, and the substituents of R ¹¹⁷ and R ¹¹⁸ are formed. In the case of the ring represented by the above general formula (4), R ¹¹¹ and R ^{112 are} preferably a hydrogen atom. R ¹¹¹ and R ^{112 of the} general formula (2), or R ¹¹⁷ and R ^{118 are} non-hydrogen atoms, and when having a substituent, since the stereoscopic effect is exhibited, the distance from the adjacent molecule in the amorphous film is changed. Large, the result may cause the drive voltage to rise. Therefore, the substituents of R ¹¹¹ and R ^{112 in} the general formula (2) are those in which R ¹¹⁷ and R ¹¹⁸ and R ¹¹⁷ and R ¹¹⁸ in the ring represented by the above general formula (4) are formed to form the above general formula ( 4) R ¹¹¹ and R ^{112 in} the ring represented by a ring are preferably a hydrogen atom.

In the above general formula (11), Ar ^{1 is} particularly preferably a phenyl group, a naphthyl group, a phenanthryl group, a 9,9-dimethylfluorenyl group or a biphenyl group.

Ra is preferably a hydrogen atom, an aryl group or a heterocyclic group.

In the present invention, the "carbon forming a ring" means a carbon atom constituting a saturated ring, an unsaturated ring or an aromatic ring. The "atom forming a ring" means a carbon atom and a hetero atom constituting a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring).

In the present invention, a hydrogen atom means an isotope having a different number of neutrals, that is, a protium, a deuterium, and a tritium.

Further, the substituent in the case of "substituted or unsubstituted" may, for example, be an aromatic hydrocarbon group, a heterocyclic group, an alkyl group (linear or branched alkyl group, cycloalkyl group, haloalkyl group) or alkoxy group as described above. Alkyl, aryloxy, aralkyl, haloalkoxy, alkylcarboxyalkyl, dialkylarylcarboxyalkyl, alkyldiarylcarbenyl, triarylcarbenyl, halogen atom, cyano , hydroxyl, nitro and carboxyl groups. Others also have alkenyl groups and alkynyl groups.

The substituents exemplified herein are preferably an aromatic hydrocarbon group, a heterocyclic group, an alkyl group, a halogen atom, an alkylcarbenyl group, an arylcarbinyl group or a cyano group. Further, in the description of each substituent, More preferred are preferred specific substituents.

"Unsubstituted" when "replaced or unsubstituted" means not taken from the foregoing The substituent is substituted and the hydrogen atom is bonded to it.

In the present specification, the "carbon number a to b" in the expression "substituted or unsubstituted carbon number a to b XX group" means that the XX group is an unsubstituted carbon number, and the XX group is not substituted. The carbon number of the substituent.

In the case of the compound described below or a partial structure thereof, the case of "substituted or unsubstituted" is also the same as described above.

Specific examples of the anthracene derivative represented by the general formula (1) are shown below, but the present invention is not limited to the above-exemplified compounds.

Moreover, the specific example of the anthracene derivative represented by the above general formula (1) is represented, for example, by the following general formula (1X).

A and B in the above general formula (1X) are shown in the following table.

The following symbols (see (10X) below) shown at the front end of the bond of the structures A and B shown in the respective columns in the above table indicate the bonding positions of the ring.

* (10X)

Therefore, for example, an anthracene derivative having the structures of A and B shown in the uppermost column of the left column of the above table is represented by the following formula.

The anthracene derivatives represented by the above general formula (1X) are similar to those described above for the structures of A and B described in the following tables.

. Dopant material

In the organic EL device of the present embodiment, the light-emitting layer contains the anthracene derivative represented by the above formula (1) and is represented by the following general formula (21). derivative. The organic EL device of the present embodiment is represented by the following general formula (21). The derivative is used as a dopant material.

In the above general formula (21), R ²⁰ to R ²⁹ are each represented by a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted meyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring.

Ar ²¹ to Ar ²⁴ in the above general formula (21) each represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, or a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms. base.

When Ar ²¹ to Ar ²⁴ in the above general formula (21) have an alkyl group as a substituent, each has at least two or more alkyl groups.

The halogen atom, the alkyl group, the aromatic hydrocarbon group, and the heterocyclic group in the above general formula (21) are, for example, those described in the above general formulas (1) to (20) and (51) to (62).

A substituted or unsubstituted methylidene group, for example, a substituted or unsubstituted linear, branched or cyclic alkylcarboxyalkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted carbon number of 6 to 30 Arylcarbylalkyl.

a linear, branched or cyclic alkylcarboxyalkyl group having 1 to 10 carbon atoms, for example, trimethylmethanyl, triethylmethane, tributylmethylalkyl, dimethylethylformane Base, dimethylisopropylmethanyl, dimethylpropylmethyl decyl, dimethyl butyl decyl, dimethyl tert-butyl decyl, diethyl isopropyl decyl, and the like.

The arylcarbenyl group having 6 to 30 carbon atoms may, for example, be phenyldimethylformamidinyl, diphenylmethylformamidinyl, diphenyl-t-butylformamyl or triphenylcarbenyl.

In the above general formula (21), R ²⁰ to R ^{29 are} preferably a hydrogen atom.

Further, in the general formula (21), it is preferred that each of Ar ²¹ to Ar ²⁴ has two or more substituents.

In the above general formula (21), at least one of Ar ²¹ to Ar ²⁴ is preferably a heterocyclic group represented by the following formula (42).

[In the above general formula (42), R ²¹¹ to R ²¹⁷ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20; Alkenyl, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted metaalkyl group, substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms or substituted or unsubstituted ring forming ring A heterocyclic group having 5 to 30 atoms.

Further, R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁶ and R ²¹⁷ are bonded to each other to form a saturated or unsaturated ring, and the rings may be Replace.

X ²¹ is selected from any of an oxygen atom or a sulfur atom.

Y ²¹ is a single bond bonded to the nitrogen atom of the above general formula (21).

The above general formula (21) is more preferably expressed by the following general formula (22).

In the above general formula (22), A ₁ to A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. An oxy, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted group A A first group of a decyl group, a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms, and a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.

p, q, r and s are each independently an integer of 0 to 3, and when p, q, r and s are each 2 or more, A ₁ to A ₄ are the same or different.

In the above general formula (22), A ₅ to A ₁₂ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted methyro group, The substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms and the substituted or unsubstituted heterocyclic group having 5 to 30 atoms forming a ring.

Further, A ₅ and A ₆ , A ₇ and A ₈ , A ₉ and A ₁₀ , and A ₁₁ and A ₁₂ may be bonded to each other to form a saturated or unsaturated ring.

In the above general formula (22), each of A ₅ to A ₁₂ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

The following shows the general formula (21) and the above general formula (22). Specific examples of the derivative, but the invention is not limited to the exemplified compounds.

In the present embodiment, the content of the dopant material in the light-emitting layer is not particularly limited, and may be appropriately selected in accordance with the purpose, and is, for example, preferably 0.1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 30% by mass. %the following. When the content of the dopant material is 0.1% by mass or more, sufficient light emission can be obtained, and when it is 70% by mass or less, concentration extinction can be avoided.

In the present embodiment, the dopant color of the dopant material contained in the light-emitting layer is not particularly limited, but a dopant material having a fluorescent property of blue light emission having a main peak wavelength of 480 nm or less is preferable. The main peak wavelength refers to the peak wavelength of the luminescence spectrum in which the luminescence intensity is maximum in the luminescence spectrum measured in a toluene solution having a concentration of 10 ^-6 mol/liter or more and 10 ^-5 mol/liter or less.

When the dopant material of the main peak wavelength is doped into the host material represented by the above general formula (1) to form a light-emitting layer, the organic EL element becomes highly efficient and has a long life.

. Combination of host material and dopant material

In the present embodiment, the host material is preferably an anthracene derivative represented by the above general formulas (5) to (10) using Z ¹ of the above general formula (1), and particularly preferably Z ^{1 is the} above general formula (8) to ((). 10) represents naphthobenzofuran. When ruthenium is substituted with naphthobenzofuran, since the planarity of naphthobenzofuran is increased, it is presumed that the packing between molecules in the light-emitting layer is increased, and thus the degree of charge mobility becomes high. At this time, electric charges are leaked from the light-emitting layer, which may lower efficiency and life. Therefore, by using a dopant having electron or hole trapping property and having a condensed ring structure, the carrier can be closed in the light-emitting layer, and high efficiency and long life can be achieved. a compound represented by the general formula (21) having an electron trapping property and having a condensed ring structure (diamine group) As a dopant material, the derivative can be used to close the electric charge in the light-emitting layer, thereby achieving high efficiency and long life.

(hole injection. conveying layer)

Hole injection. The transport layer helps the hole to be injected into the light-emitting layer and is transported to the layer of the light-emitting region, and a compound having a large hole mobility and a small ionization energy can be used.

Forming a hole injection. The material of the transport layer, preferably a lower electric field strength, is preferably a material for transporting the holes to the light-emitting layer, for example, an aromatic amine compound.

(electron injection. transport layer)

Electron injection. The transport layer is a layer that allows electrons to be injected into the light-emitting layer and transported to the light-emitting region, and a compound having a large electron mobility can be used.

Electron injection. The compound for the transport layer is preferably an aromatic heterocyclic compound having one or more hetero atoms in the molecule, and particularly preferably a nitrogen-containing ring derivative. The nitrogen-containing cyclic derivative is preferably a heterocyclic compound having a nitrogen-containing 6-membered ring or a 5-membered ring skeleton.

In the organic EL device of the present invention, the organic layer other than the light-emitting layer may be selected from any of the materials used in the conventional organic EL device in addition to the compounds exemplified above.

(substrate)

The organic EL device of the present embodiment is fabricated on a light-transmissive substrate. The light-transmitting substrate supports a substrate constituting an anode, an organic layer, a cathode, or the like of the organic EL element, and preferably has a light transmittance of 50% or more in a visible light region of 400 nm or more and 700 nm or less, and is a smooth substrate.

The light-transmitting substrate is, for example, a glass plate, a polymer plate or the like.

The glass plate is, for example, especially soda lime glass, containing bismuth. Glass of bismuth, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz are used as raw materials.

The polymer sheet is, for example, polycarbonate, acrylic acid, polyethylene terephthalate, polythioether, polyfluorene or the like as a raw material.

(anode and cathode)

The anode of the organic EL element serves as a function of injecting a hole into the light-emitting layer, and is more effective in having a work function of 4.5 eV or more.

Specific examples of the anode material are indium tin oxide alloy (ITO), tin oxide. (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like.

When the light emitted from the light-emitting layer is taken out from the anode side, it is preferred that the light transmittance of the visible light region of the anode is greater than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω/□ (Ω/sq) or less. The film thickness of the anode varies depending on the material, but is usually 10 nm or more and 1 μm or less, preferably 10 nm or more and 200 nm or less.

In order to inject electrons into the light-emitting layer, the cathode preferably has a work function of a small material.

The cathode material is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-niobium-lithium alloy, magnesium-silver alloy, or the like can be used.

Similarly to the anode, the cathode can be formed into a thin film on the electron transport layer or the electron injection layer by a vapor deposition method or the like. Further, a form in which light emitted from the light-emitting layer is taken out from the cathode side may be employed. When the light emitted from the light-emitting layer is taken out from the cathode side, the light transmittance in the visible light region of the cathode is preferably more than 10%.

The sheet resistance of the cathode is preferably several hundred Ω/□ or less.

The film thickness of the cathode varies depending on the material, but is usually 10 nm or more and 1 μm or less, and preferably 50 nm or more and 200 nm or less.

(Method of Forming Each Layer of Organic EL Element)

The method for forming each layer of the organic EL device of the present embodiment is not particularly limited. A conventionally known method of forming a vacuum vapor deposition method, a spin coating method, or the like can be used. The organic layer used in the organic EL device of the present embodiment The method may be a vacuum deposition method, a molecular beam evaporation method (MBE method, MBE; Molecular Beam Epitaxy) or a dip coating method in which a solution dissolved in a solvent, a spin coating method, a casting method, a bar coating method, or the like. It is formed by a well-known method of the coating method, such as a roll coating method.

(Thickness of each layer of the organic EL element)

The film thickness of the light-emitting layer is preferably 5 nm or more and 50 nm or less, more preferably 7 nm or more and 50 nm or less, and most preferably 10 nm or more and 50 nm or less. The film thickness of the light-emitting layer is 5 nm or more, and it becomes easy to form a light-emitting layer, and it is easy to adjust the chromaticity. The film thickness of the light-emitting layer is 50 nm or less, and the increase in the driving voltage can be suppressed.

The film thickness of each of the other organic layers is not particularly limited, but is usually in the range of several nm to 1 μm. In such a film thickness range, defects such as pinholes caused by an excessively thin film thickness can be prevented, and an increase in driving voltage due to an excessive thickness can be suppressed, and deterioration in efficiency can be prevented.

[Second Embodiment]

Next, an organic EL device of the second embodiment will be described.

In the organic EL device of the present embodiment, the compound contained in the light-emitting layer is an anthracene derivative represented by the above formula (1) and an anthracene derivative represented by the following general formula (41), and the first embodiment The organic EL elements are different. In other respects, the organic EL device of the second embodiment is the same as the organic EL device of the first embodiment. Further, in the second embodiment, materials or compounds not specifically mentioned may be used as described in the first embodiment. The same material or compound. In the organic EL device of the second embodiment, a preferred compound such as an anthracene derivative contained in the light-emitting layer or a substituent thereof is also the same as that described in the first embodiment. Further, the schematic configuration of the organic EL element of the second embodiment is also the same as that shown in FIG. 1.

(lighting layer)

In the organic EL device of the present embodiment, the light-emitting layer contains the anthracene derivative represented by the above formula (1) and the anthracene derivative represented by the following general formula (41).

. Dopant material

In the organic EL device of the present embodiment, the anthracene derivative represented by the following general formula (41) can be used as a dopant material, and the anthracene derivative represented by the above general formula (1) can be used as a host material.

In the above general formula (41), R ²¹ to R ²⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted meyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 30, wherein Ar ²¹ to Ar ²⁴ in the above general formula (41) each represent a substituted or unsubstituted aromatic ring having a carbon number of 6 to 30. a hydrocarbon group, or a substituted or unsubstituted heterocyclic group having 5 to 30 atomic atoms forming a ring.

However, at least one of Ar ²¹ to Ar ²⁴ in the above general formula (41) is a heterocyclic group represented by the following formula (42).

In the above general formula (42), R ²¹¹ to R ²¹⁷ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20 carbon atoms. a substituted, unsubstituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted metaalkyl group, a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring-forming ring. A heterocyclic group having 5 to 30 atoms.

Further, in the above general formula (42), R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁶ and R ²¹⁷ are bonded to each other to form a saturated or unsaturated group. Rings, such rings can be replaced.

In the above general formula (42), X ²¹ is selected from any one of an oxygen atom or a sulfur atom.

In the above general formula (42), y ²¹ is a single bond bonded to the nitrogen atom of the above general formula (41).

The halogen atom, aromatic hydrocarbon group, heterocyclic group, alkyl group, alkoxy group, aryloxy group, arylthio group or arylamine group in the above general formulas (41) and (42), for example, have the above general formula ( 1) ~(20), (51)~(62) The groups described.

The methylidene group in the above general formulas (41) and (42), for example, an unsubstituted methyroalkyl group, for example, an alkylmercaptoalkyl group having 1 to 30 carbon atoms and an arylmethylalkyl group having 6 to 60 carbon atoms. .

The alkylmercaptoalkyl group having 1 to 30 carbon atoms, for example, a trialkylcarbenyl group having an alkyl group exemplified by the above alkyl group having 1 to 20 carbon atoms, specifically, for example, trimethylcarbinyl group, or Ethylmethylation, tri-n-butylcarboxyalkyl, tri-n-octylcarboxyalkyl, triisobutylcarboxyalkyl, dimethylethylformamidinyl, dimethylisopropylformamidinyl, Methyl-n-propylcarboxyalkyl, dimethyl-n-butylcarboxyalkyl, dimethyl-t-butylformamidinyl, diethylisopropylformamidinyl, vinyl dimethylformamidinyl, Propyl dimethylformamyl, triisopropylcarbylalkyl and the like. Each of the three alkyl groups may be the same or different.

An arylcarbenyl group having a carbon number of 6 to 60 formed by a ring, for example, an arylcarbenyl group, an alkylarylcarbenyl group, a dialkylarylcarbenyl group, a diarylmethylalkyl group, an alkyl group Arylcarboxyalkyl, triarylcarbinyl. The plural aryl groups may be the same or different from each other or the alkyl groups.

a dialkyl aryl methantylene group, for example, an alkyl group having two alkyl groups having the above carbon number of 1 to 20, and having one of the above-mentioned aromatic hydrocarbon groups having 6 to 30 carbon atoms forming a ring Alkylarylcarboxyalkyl. The carbon number of the dialkylarylmethanyl group is preferably from 8 to 30. The two alkyl groups may be the same or different.

The alkyl diarylcarbinyl group has, for example, an alkyl group having one alkyl group having 1 to 20 carbon atoms as described above, and having two aromatic hydrocarbon groups having 6 to 30 carbon atoms forming the ring. Alkyl diarylcarbenyl. The carbon number of the alkyldiarylcarbenyl group is preferably from 13 to 30. The two aryl groups may each be the same or different.

The triarylcarbinyl group is, for example, a triarylcarbenyl group having three of the above-mentioned aromatic hydrocarbon groups having 6 to 30 carbon atoms forming a ring. The carbon number of the triarylcarbenyl group is preferably from 18 to 30. The three aryl groups may each be the same or different.

Such an arylcarbenyl group is, for example, phenyldimethylformamidinyl, diphenylmethylformamidine, diphenyl-t-butylformamyl, or triphenylcarbenyl.

The alkenyl group having 2 to 20 carbon atoms in the above general formula (42) may be any of a straight chain, a branched chain or a cyclic group, for example, a vinyl group, a propenyl group, a butenyl group, an oil group, and a 20 carbon five. Alkenyl (icosapentaenyl), docosahexenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2- Propylene and the like. Among the above alkenyl groups, a vinyl group is preferred.

The alkynyl group having 2 to 20 carbon atoms in the above general formula (42) may be any of a straight chain, a branched chain or a cyclic group, and examples thereof include an ethynyl group, a propynyl group, a 2-phenylethynyl group and the like. Among the above alkynyl groups, an ethynyl group is preferred.

In the above general formula (42), R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁶ and R ²¹⁷ are bonded to each other to form a saturated or unsaturated ring. For example, a cycloalkane, a cyclopentane, a cyclopentene, a cyclohexene, a cycloheptene having a ring number of 4 to 12, such as cyclobutane, cyclopentane, cyclohexane, adamantane or norbornane. a cycloalkane, a benzene, a naphthalene having a carbon number of 4 to 12, such as a cyclic olefin having 4 to 12 carbon atoms, a cyclohexadiene, a cycloheptadiene or a cyclooctadiene formed by a cyclooctene or the like. , Philippine, 蒽, 芘, An aromatic ring having a carbon number of 6 to 50 which forms a ring such as a terpene. Further, the substituent is, for example, the same as the above examples.

In the above general formula (41), Ar ²¹ and Ar ^{23 are} preferably a heterocyclic group represented by the above general formula (42).

In the above general formula (41), R ²¹ to R ^{28 are} preferably a hydrogen atom.

R ²² and R ^{26 in the} above general formula (41) are a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkylcarbenyl group having 3 to 30 carbon atoms, R ²¹ and R ^{23 .} R ²⁴ , R ²⁵ , R ²⁷ and R ^{28 are more} preferably a hydrogen atom.

Further, X ^{21 of the} above general formula (42) is preferably an oxygen atom.

Particularly preferably, Ar ²¹ to Ar ²⁴ in the above general formula (41) are represented by the above general formula (42), and X ²¹ is an oxygen atom.

A preferred embodiment of the compound represented by the above formula (41) is, for example, represented by the following general formula (43).

In the above general formula (43), R ²¹ to R ²⁸ each represent a hydrogen atom, a halogen atom, a cyano-substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted methyroalkyl group, or a substituted or none. Substituted to form an aromatic hydrocarbon group having 6 to 30 carbon atoms, R ²¹⁸ to R ²⁴¹ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted. Alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted methylosyl group, substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms, Or a substituted or unsubstituted heterocyclic group having 5 to 30 atoms in the ring.

X ²² and X ²³ are selected from either an oxygen atom or a sulfur atom.

The halogen atom, aromatic hydrocarbon group, heterocyclic group, alkyl group, alkoxy group, aryloxy group, arylthio group or arylamine group in the above general formula (43), for example, has the above general formula (1) to ( 20), the groups described in (51) ~ (62).

The mercaptoalkyl group in the above general formula (43) is, for example, a group described in the above general formulas (41) and (42).

The alkenyl group having 2 to 20 carbon atoms in the above general formula (43) and the alkynyl group having 2 to 20 carbon atoms in the above general formula (43) are, for example, described in the above general formulas (41) and (42). Group.

In the above general formula (43), R ²¹ to R ^{28 are} preferably a hydrogen atom.

R ²² and R ^{26 in the} above general formula (43) are a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkylcarbenyl group having 3 to 30 carbon atoms, R ²¹ and R ^{23 .} R ²⁴ , R ²⁵ , R ²⁷ and R ^{28 are more} preferably a hydrogen atom.

Further, X ²² and X ^{23 of the} above general formula (43) are preferably an oxygen atom.

Further, in a preferred embodiment of the above general formula (43), for example, R ²²¹ and R ²²⁸ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring. An aromatic hydrocarbon group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 atomic number of atoms.

Further, in a preferred embodiment of the above general formula (43), for example, 0, 1 or 2 of R ²³² to R ²³⁶ are selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or substituted or unsubstituted. The ring forms a carbon number of 6 to 30 aromatic hydrocarbon groups, and 0, 1 or 2 of R ²³⁷ to R ²⁴¹ are selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or substituted or absent. Substituting an aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring.

Specific examples of the anthracene derivative represented by the above general formula (41) are shown below, but the present invention is not limited to the above-exemplified compounds.

In the present embodiment, the content of the dopant material in the light-emitting layer is not particularly limited, and may be appropriately selected in accordance with the purpose, and is, for example, preferably 0.1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 30% by mass. %the following. When the content of the dopant material is 0.1% by mass or more, sufficient light emission can be obtained, and when it is 70% by mass or less, concentration extinction can be avoided.

In the present embodiment, the dopant color of the dopant material contained in the light-emitting layer is not particularly limited, but a dopant material having a fluorescent property of blue light emission having a main peak wavelength of 480 nm or less is preferable. The main peak wavelength refers to the peak wavelength of the luminescence spectrum in which the luminescence intensity in the luminescence spectrum measured in the toluene solution having a concentration of 10 ^-6 mol/liter or more and 10 ^-5 mol/liter or less is the maximum.

When the dopant material of the main peak wavelength is doped into the host material represented by the above general formula (1) to form a light-emitting layer, the organic EL element becomes highly efficient and has a long life.

. Combination of host material and dopant material

In the present embodiment, the host material is preferably an anthracene derivative represented by the above general formulas (5) to (10) using Z ¹ of the above general formula (1), and particularly preferably Z ^{1 is the} above general formula (8) to ((). 10) represents naphthobenzofuran. When naphthobenzofuran is substituted for hydrazine, it is presumed that due to the planarity of naphthobenzofuran, the packing between the molecules in the light-emitting layer is improved, and thus the degree of charge mobility becomes high. At this time, electric charges are leaked from the light-emitting layer, which may lower efficiency and life. Therefore, by using a dopant having electron or hole trapping property and having a condensed ring structure, a carrier can be enclosed in the light-emitting layer, and high efficiency and long life can be achieved. When a compound (diamine fluorene derivative) represented by the general formula (41) having an electron-trapping property and having a condensed ring structure is used as a dopant material, the charge can be enclosed in the light-emitting layer, and high efficiency can be achieved. Long life.

[Modification of Embodiment]

The present invention is not limited to the above-described embodiments, and modifications, improvements, etc., which are within the scope of the invention, are included in the present invention.

The light-emitting layer is not limited to one layer, and a plurality of light-emitting layers may be laminated. When the organic EL device has a plurality of light-emitting layers, at least one of the light-emitting layers may contain a compound represented by the above formula (1) and a compound represented by the above general formula (21) or the general formula (41), and other light-emitting layers may be used. The layer may be a fluorescent light emitting layer or a phosphorescent emitting layer.

Further, when the organic EL element has a plurality of light-emitting layers, the light-emitting layers may be disposed adjacent to each other or may be laminated with a plurality of light-emitting units, that is, tandem organic EL elements.

In the present invention, the light-emitting layer preferably contains a charge injection auxiliary agent.

When a light-emitting layer is formed using a host material having a wide energy gap, the difference between the ionization energy ( Ip : ionization potential) of the host material and the Ip of the hole injection and transport layer becomes large, and it becomes difficult to inject the light-emitting layer into the hole. There is a concern that the driving voltage required to obtain sufficient brightness rises.

In this case, the hole is easily injected into the light-emitting layer by injecting a charge injecting and transporting a charge into the light-emitting layer, thereby lowering the driving voltage.

The charge injection auxiliary agent can be, for example, a general hole injection, a material to be transported, or the like.

Specific examples thereof include a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyaralkyl derivative, a pyrazoline derivative, and a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, and an amine group. Instead of a chalcone derivative, an oxazole derivative, an anthrone derivative, an anthracene derivative, an anthracene derivative, a decane derivative, a polydecane system, an aniline copolymer, or a conductive polymer oligomer (especially Thiophene oligomers) and the like.

The material for the hole injecting property is, for example, the above, preferably a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, and particularly preferably an aromatic tertiary amine compound.

Further, there are two condensed aromatic rings in the molecule, for example, 4,4'-bis(N-(1-naphthyl)-N-phenylamino)biphenyl (hereinafter abbreviated as NPD), and the triphenylamine units are bonded to 3 4,4',4"-tris(N-(3-methylphenyl)-N-phenylamino)triphenylamine (hereinafter referred to as MTDATA).

Further, a hexaazatriphenylene derivative or the like can also be suitably used as a material for hole injectability.

Further, an inorganic compound such as p-type Si or p-type SiC can also be used as a hole injecting material.

The organic EL device of the present invention can be suitably used as a display device for a television, a mobile phone, or a personal computer, or an electronic device such as a lighting device or a lighting device for a vehicle lamp.

[Examples]

Next, an embodiment of the present invention will be described, but the present invention is not limited to the embodiments.

[Synthesis of Compounds] Synthesis Example 1 Synthesis of Compound 1

According to the following scheme (Scheme) Synthesis of compound 1.

(1-1) Synthesis of 4-phenyl-2-methylaniline

4-bromo-2-methylaniline (5.00 g), phenylboronic acid (4.26 g), hydrazine (triphenylphosphine) palladium (0) (1.60 g), toluene (67 mL), 1, under argon atmosphere. 2-two A mixture of methoxyethane (67 mL) and aq. After the resulting reaction mixture was cooled to room temperature, it was extracted with toluene. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The residue obtained was purified by silica gel column chromatography to give 4-phenyl-2-methylaniline (4.74 g). The yield was 96%.

Synthesis of (1-2) N-(2-methyl-4-phenylphenyl)dibenzofuran-4-amine

4-phenyl-2-methylaniline (4.50 g), 4-bromodibenzofuran (3.20 g), and tris(benzylideneacetone) II obtained in (1-1) under an argon atmosphere Palladium (0) (0.18 g), BINAP (2,2'-bis(diphenylphosphino)-1,1'-bisnaphthyl) (0.24 g), sodium-t-butoxide ( A mixture of 2.50 g) and toluene (87 mL) was refluxed at 90 ° C for 8 hours. The obtained reaction mixture was cooled to room temperature, filtered over Celite, and evaporated. The residue thus obtained was purified by silica gel column chromatography to give N-(2-methyl-4-phenylphenyl)dibenzofuran-4-amine (3.28 g). The yield was 72%.

(1-3) Synthesis of Compound 1

N-(2-methyl-4-phenylphenyl)dibenzofuran-4-amine (3.26 g) and 1,6-dibromofluorene (1.40 g) obtained in (1-2) under an argon atmosphere. a mixture of tris(dibenzylideneacetone)dipalladium(0) (0.11 g), tri-t-butylphosphine (0.08 g), sodium-t-butoxide (2.50 g) and toluene (19 mL), Stir at 85 ° C for 8 hours. The obtained reaction mixture was cooled to room temperature, filtered over Celite, and evaporated. The residue thus obtained was purified by silica gel column chromatography and recrystallization to give Compound 1 (2.54 g). The yield was 73%. The obtained compound uses mass spectrometry The mass spectrometry (MS) confirmed that m/e = 896 with respect to the molecular weight of 896.34.

Synthesis Example 2 Synthesis of Compound 2

In Synthesis Example 1, except that 4-bromo-3-methylaniline was used instead of 4-bromo-2-methylaniline, the same operation was carried out to obtain Compound 2. The obtained compound was confirmed by a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 3 Synthesis of Compound 3

In Synthesis Example 1, except that 5-bromo-2-methylaniline was used instead of 4-bromo-2-methylaniline, the same operation was carried out to obtain Compound 3. The obtained compound was confirmed by a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 4 Synthesis of Compound 4

In Synthesis Example 1, except that 3-bromo-2-methylaniline was used instead of 4-bromo-2-methylaniline, the same operation was carried out to obtain Compound 4. The obtained compound was confirmed by a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 5 Synthesis of Compound 5

In Synthesis Example 1, except that 3-bromo-4-methylaniline was used instead of 4-bromo-2-methylaniline, the same operation was carried out to obtain Compound 5. The obtained compound was confirmed by a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 6 Synthesis of Compound 6

In Synthesis Example 1, except that 2-bromo-4-methylaniline was used instead of 4-bromo-2-methylaniline, the same operation was carried out to give Compound 6. The obtained compound was confirmed by a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Intermediate Synthesis Example 1 Synthesis of Intermediate A

According to the following scheme (Scheme) Synthesis of Intermediate A.

Synthesis of (A-1) 4-phenyldibenzofuran

4-bromodibenzofuran (400 g), phenylboronic acid (267 g), hydrazine (triphenylphosphine) palladium (0) (56.2 g), sodium carbonate (515 g), 1,2-di under argon atmosphere A mixture of methoxyethane (4000 mL) and water (2340 mL) was refluxed for 16 h. The obtained reaction mixture was cooled to room temperature and then extracted with ethyl acetate. The residue obtained was purified by silica gel column chromatography to give 4-phenyldibenzofuran (383 g). The yield was 97%.

(A-2) Synthesis of Intermediate A

A solution of 4-phenyldibenzofuran (250 g) obtained in (A-1) in tetrahydrofuran (1875 mL) was cooled to -10 ° C under argon atmosphere, and 1.6 M n-butyllithium hexane solution (704 mL) was dropped. The reaction solution was stirred at 10 ° C for 1.5 hours. The reaction liquid was cooled to -60 ° C, and 1,2-dibromoethane (289 g) was added dropwise, and the reaction liquid was returned to room temperature, and stirred for 1 day. Water was added to the obtained reaction mixture, and extracted with ethyl acetate. The residue obtained was purified by silica gel column chromatography and recrystallization to afford Intermediate A (137 g). The yield was 41%.

Synthesis Example 7 Synthesis of Compound 7

According to the following scheme (Scheme) Synthesis of compound 7.

Synthesis of (7-1) 6-phenyl-N-(p-tolyl)dibenzofuran-4-amine

P-toluidine (7.59 g), Intermediate A (11.45 g) obtained in Intermediate Synthesis Example 1, tris(dibenzylideneacetone) dipalladium (0) (0.49 g), BINAP (0.66 g) under argon atmosphere A mixture of sodium-t-butoxide (6.81 g) and toluene (177 mL) was refluxed at 90 ° C for 6.5 hours. The obtained reaction mixture was cooled to room temperature, filtered over Celite, and evaporated. The residue obtained was purified by silica gel column chromatography to give 6-phenyl-N-(p-tolyl)dibenzofuran-4-amine (11.12 g). The yield was 90%.

(7-2) Synthesis of Compound 7

6-phenyl-N-(p-tolyl)dibenzofuran-4-amine (11.12 g) and 1,6-dibromofluorene (4.77) obtained in (7-1) under an argon atmosphere. g), a mixture of tris(dibenzylideneacetone)dipalladium(0) (0.36 g), tri-t-butylphosphine (0.27 g), sodium-t-butoxide (3.81 g) and toluene (66 mL) , reflux for 8 hours. The obtained reaction mixture was cooled to room temperature, and methanol (132 mL) was added, and after stirring, the mixture was filtered to obtain a precipitate. The obtained filtrate was purified by silica gel column chromatography and recrystallization to give Compound 7 (9.19 g). The yield was 77%. The obtained compound was confirmed using a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 8 Synthesis of Compound 8

In Synthesis Example 7, except that m-toluidine was used instead of p-toluidine, the same operation was carried out to obtain Compound 8. The obtained compound was confirmed using a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 9 Synthesis of Compound 9

In Synthesis Example 7, except that o-toluidine was used instead of p-toluidine, the same operation was carried out to obtain Compound 9. The obtained compound was confirmed using a mass spectrometer, m/e = 896 with respect to a molecular weight of 896.34.

Synthesis Example 10 Synthesis of Compound 10

In Synthesis Example 7, except that 3,5-dimethylaniline was used instead of p-toluidine, the same procedure was carried out to obtain Compound 10. The obtained compound was confirmed using a mass spectrometer, m/e = 924 with respect to a molecular weight of 924.37.

Synthesis Example 11 Synthesis of Compound 11

In Synthesis Example 7, except that 3,4-dimethylaniline was used instead of p-toluidine, the same operation was carried out to obtain Compound 11. The obtained compound was confirmed using a mass spectrometer, m/e = 924 with respect to a molecular weight of 924.37.

[Manufacture of Organic EL Elements]

The compounds used are as follows.

(Example 1)

A glass substrate (manufactured by Geomatec Co., Ltd.) having a thickness of 25 mm × 75 mm × 1.1 mm and having an ITO transparent electrode (anode) was ultrasonically washed in isopropyl alcohol for 5 minutes, and then washed by UV ozone for 30 minutes. The film thickness of ITO was 130 nm.

The glass substrate with the transparent electrode wire after the cleaning is attached to the substrate holder of the vacuum vapor deposition apparatus. First, the compound HA-1 is vapor-deposited on the surface on the side where the transparent electrode line is formed to form a film thickness of 5 nm. Compound HA-1 Membrane to cover the transparent electrode. This HA-1 film functions as a hole injection layer.

After the film formation of the HA-1 film, the compound HT-1 was vapor-deposited, and an HT-1 film having a film thickness of 95 nm was formed on the HA-1 film. This HT-1 film functions as a hole transport layer.

Next, the compound BH-1 (host material) and the compound BD-1 (dopant material) were co-deposited on the HT-1 film to form a light-emitting layer film having a film thickness of 25 nm. In the light-emitting layer, the host material concentration was 95% by mass, and the dopant material concentration was 5% by mass.

The electron transporting compound ET-1 was deposited on the light emitting layer to form an electron transporting layer having a film thickness of 25 nm.

LiF was deposited on this electron transport layer to form a LiF layer having a thickness of 1 nm.

Metal Al was vapor-deposited on this LiF film to form a cathode of metal Al having a thickness of 80 nm.

(Example 2)

In the organic EL device of Example 2, an organic EL device was produced in the same manner as in Example 1 except that the material constituting the light-emitting layer was changed to the compound BH-1 (host material) and the compound BD-2 (dopant material).

(Comparative examples 1 to 4)

In the organic EL devices of Comparative Examples 1 to 4, as shown in Table 11, an organic EL device was produced in the same manner as in Example 1 except that the materials in the light-emitting layer were changed.

[Evaluation of Organic EL Elements]

For the organic EL element after fabrication, a voltage was applied to make the current density 10 mA/cm ² , and then the driving voltage, CIE 1931 chromaticity, current efficiency L/J, external quantum efficiency EQE, and main peak wavelength λ _{p were} evaluated. Further, a voltage was applied to make the current density 50 mA/cm ² , and then the life LT90 was evaluated. The results are shown in Table 11. For each of the evaluation items other than the CIE 1931 chromaticity and the main peak wavelength λ _p , the ratio of the values of the evaluation items of Examples 1 and 2 and Comparative Examples 1 to 4 to the values of the respective evaluation items of Comparative Example 1 was calculated. value.

. Driving voltage

The current density was set to 10 mA/cm ² , and the voltage (unit: V) at the time of energization between the ITO transparent electrode and the metal Al cathode was measured.

. CIE1931 color

The current density was set to 10 mA/cm ² , and the CIE 1931 chromaticity coordinates (x, y) when a voltage was applied to the element were measured using a spectroradiometer CS-1000 (manufactured by Konica Minolta Co., Ltd.).

. Current efficiency L/J

The current density was set to 10 mA/cm ² , and the spectral radiance spectrum when the voltage was applied to the element was measured by the above-described spectral radiance measurement, and the current efficiency (unit: cd/A) was calculated from the obtained spectral luminescence spectrum.

. External quantum efficiency EQE

From the above-mentioned spectral radiance spectrum, it is assumed that Lambert has been performed. (Lambertian) The external quantum efficiency EQE (unit: %) was calculated by radiation.

. Main peak wavelength λ _p

From the obtained spectral radiance spectrum, the main peak wavelength λ _p (unit: nm) was obtained.

. Life LT90

When the current density was 50 mA/cm ² , the voltage was applied to the element, and the time until the initial brightness was measured was 90% (unit: h).

In the above-mentioned Example 1, the anthracene derivative represented by the above general formula (1) is used as a host material, and is represented by the above general formula (21). The organic EL device used as the dopant material of the derivative has a lower voltage than the comparative example 1 using the host material and the dopant material other than the above, but can greatly improve the efficiency and the lifetime.

In the same manner, the above-mentioned Example 2 is an organic EL device in which the anthracene derivative represented by the above general formula (1) is used as a host material, and the anthracene derivative represented by the above general formula (41) is used as a dopant material. In Comparative Example 1, the voltage was lower, but the efficiency and life were greatly improved.

In Comparative Example 2, an organic EL device using the same host material as in Example 1 and Example 2 was used.

In Comparative Example 3 and Comparative Example 4, an organic EL device having a ruthenium compound having a different structure from the general formula (1).

In the organic EL devices of the first embodiment and the second embodiment, even when compared with the comparative examples 2 to 4, the low voltage can be maintained, and the efficiency and the life can be further improved. In particular, Example 1 was driven at the same low voltage as compared with Comparative Example 2, but the efficiency and life were greatly improved. Further, in the second embodiment, the second embodiment is driven at the same low voltage as compared with the second comparative example, but the external quantum efficiency EQE and the lifetime can be greatly improved.

1‧‧‧ cathode

2‧‧‧Electronic transport layer

3‧‧‧Lighting layer

4‧‧‧ hole transport layer

5‧‧‧Anode

6‧‧‧Substrate

Claims (18)

An organic electroluminescence device comprising: a cathode; an anode; and an organic layer disposed between the cathode and the anode and containing at least one or more of the light-emitting layers; and the light-emitting layer is represented by the following general formula (1) And the derivative thereof is represented by the following general formula (21) derivative, [In the above general formula (1), any of R ¹ ~ R ¹⁰ c departments for bonded to L ¹ is a single bond, is not used to L ¹ bonded to R ¹ ~ R ¹⁰ are each selected from a hydrogen atom , halogen atom, hydroxyl group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted The aryloxy group having 6 to 30 carbon atoms forming a ring, the substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, the substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, Or a substituted or unsubstituted heterocyclic group having 5 to 30 atomic number of the ring forming ring, and L ¹ is selected from any one of a single bond or a linking group, and the number of carbon atoms forming the ring in which the above linking group is substituted or unsubstituted 6 to 30 (a+1) of an aromatic hydrocarbon group, a substituted or unsubstituted ring-forming atomic group having 5 to 30 (a+1)-valent heterocyclic group, or the aforementioned substituted or unsubstituted ring forming ring An aromatic hydrocarbon group having 6 to 30 carbon atoms and a (a+1)-valent group formed by the bonding of 2 to 4 groups selected from the above-mentioned substituted or unsubstituted heterocyclic group having 5 to 30 atomic groups forming a ring, a, b, c each represent an integer of 1 to 4, Z ¹ following a line Represented by the formula (2)] [In the above general formula (2), X ¹ is selected from any one of an oxygen atom or a sulfur atom, and each of R ¹¹¹ to R ¹¹⁸ is not used in the above general formula (1), and is not used for R ¹ bonded to L ¹ . R ^{10 is} synonymous, but R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹¹⁷ or 2 of R ¹¹⁷ and R ¹¹⁸ are adjacent to each other. a substituent, which is bonded to each other to form a ring represented by the following general formula (3) or (4)] [In the above general formula (3), y ¹ and y ² represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2), and in the above general formula (4), y ³ and y ^{4 are} selected from the group consisting of y ³ and y ^{4 .} The bonding positions of R ¹¹¹ to R ¹¹⁸ of the above general formula (2), R ¹²¹ to R ¹²⁴ and R ¹²⁵ to R ¹²⁸ are each not in the above general formula (1), and are not used for R ¹ bonding with L ¹ . R ^{10 is} synonymous, and X ² is selected from any one of an oxygen atom or a sulfur atom. In the above general formula (2), R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²¹ to R ¹²⁴ of the above general formula (3) In one or the above general formula (2), any of R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²⁵ to R ¹²⁸ of the above general formula (4) are single bonds, and are used for L of the above general formula (1). ¹ bond knot] [In the above general formula (21), R ²⁰ to R ²⁹ are each represented by a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted methyroalkyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and Ar ²¹ to Ar ²⁴ each represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, or a substituted or a The heterocyclic group having 5 to 30 atoms in the form of a ring is substituted, and when Ar ²¹ to Ar ²⁴ have an alkyl group as a substituent, each has at least two or more alkyl groups]. An organic electroluminescence device comprising: a cathode; an anode; and an organic layer disposed between the cathode and the anode and containing at least one or more of the light-emitting layers; and the light-emitting layer is represented by the following general formula (1) a hydrazine derivative and an anthracene derivative represented by the following general formula (41), [In the above general formula (1), any of R ¹ ~ R ¹⁰ c departments for bonded to L ¹ is a single bond, is not used to L ¹ bonded to R ¹ ~ R ¹⁰ are each selected from a hydrogen atom , halogen atom, hydroxyl group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted The aryloxy group having 6 to 30 carbon atoms forming a ring, the substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, the substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, Or a substituted or unsubstituted heterocyclic group having 5 to 30 atomic number of the ring forming ring, and L ¹ is selected from any one of a single bond or a linking group, and the number of carbon atoms forming the ring in which the above linking group is substituted or unsubstituted 6 to 30 (a+1) of an aromatic hydrocarbon group, a substituted or unsubstituted ring-forming atomic group having 5 to 30 (a+1)-valent heterocyclic group, or the aforementioned substituted or unsubstituted ring forming ring An aromatic hydrocarbon group having 6 to 30 carbon atoms and a (a+1)-valent group formed by the bonding of 2 to 4 groups selected from the above-mentioned substituted or unsubstituted heterocyclic group having 5 to 30 atomic groups forming a ring, a, b, and c each represent an integer from 1 to 4, and Z ^{1 is one} of the following General expression (2) means] [In the above general formula (2), X ¹ is selected from any one of an oxygen atom or a sulfur atom, and each of R ¹¹¹ to R ¹¹⁸ is not used in the above general formula (1), and is not used for R ¹ bonded to L ¹ . R ^{10 is} synonymous, but R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹¹⁷ or 2 adjacent to at least one of R ¹¹⁷ and R ¹¹⁸ a substituent, which is bonded to each other to form a ring represented by the following general formula (3) or (4)] [In the above general formula (3), y ¹ and y ² represent a bonding position selected from R ¹¹¹ to R ¹¹⁸ of the above general formula (2), and in the above general formula (4), y ³ and y ^{4 are} selected from the group consisting of y ³ and y ^{4 .} The bonding positions of R ¹¹¹ to R ¹¹⁸ of the above general formula (2), R ¹²¹ to R ¹²⁴ and R ¹²⁵ to R ¹²⁸ are each not in the above general formula (1), and are not used for R ¹ bonding with L ¹ . R ^{10 is} synonymous, and X ² is selected from any one of an oxygen atom or a sulfur atom. In the above general formula (2), R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²¹ to R ¹²⁴ of the above general formula (3) In one or the above general formula (2), any of R ¹¹¹ to R ¹¹⁸ which does not form a ring, and R ¹²⁵ to R ¹²⁸ of the above general formula (4) are single bonds, and are used for L of the above general formula (1). ¹ bond knot] [In the above general formula (41), R ²¹ to R ²⁸ are each represented by a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted methyroalkyl group (silyl). Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and Ar ²¹ to Ar ²⁴ each represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms forming a ring, or a substituted or a In the above general formula (41), at least one of Ar ²¹ to Ar ²⁴ is a heterocyclic group represented by the following formula (42), which is substituted with a heterocyclic group having 5 to 30 atoms. [In the above general formula (42), R ²¹¹ to R ²¹⁷ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20; Alkenyl, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted metaalkyl group, substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms or substituted or unsubstituted ring forming ring a heterocyclic group having 5 to 30 atoms, and R ²¹¹ and R ²¹² , R ²¹² and R ²¹³ , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁶ and R ²¹⁷ may be bonded to each other to form a saturated or An unsaturated ring, such a ring may be substituted, and X ²¹ is selected from any one of an oxygen atom or a sulfur atom, and y ²¹ is a single bond bonded to the nitrogen atom of the above general formula (41)]. The organic electroluminescence device according to claim 1 or 2, wherein Z ¹ in the above general formula (1) is represented by any one of the following general formulas (5) to (7), [In the above general formulas (5) to (7), R ¹³¹ to R ¹⁴⁰ , R ¹⁴¹ to R ¹⁵⁰ , and R ¹⁵¹ to R ¹⁶⁰ are each not in the above general formula (1), and are not used for bonding to L ¹ . ¹ to R ^{10 are} synonymous, but any of R ¹³¹ to R ¹⁴⁰ , any of R ¹⁴¹ to R ¹⁵⁰ , and any of R ¹⁵¹ to R ¹⁶⁰ are used for bonding with L ¹ and for bonding with L ¹ the group is a single bond, X ^1, X ² are each the aforementioned general formula (2) in the X ^1, the (4) in the same meaning as the general formula X ^2, identical or different X ¹ and X ² Department]. The organic electroluminescence device according to claim 1 or 2, wherein Z ¹ in the above general formula (1) is represented by any one of the following general formulas (8) to (10), [In the above general formulas (8) to (10), R ¹⁶¹ to R ¹⁷⁰ , R ¹⁷¹ to R ¹⁸⁰ , and R ¹⁸¹ to R ¹⁹⁰ each are the same as those in the above general formula (1), which are not used for bonding with L ¹ . ¹ to R ^{10 are} synonymous, but any of R ¹⁶¹ to R ¹⁷⁰ , any of R ¹⁷¹ to R ¹⁸⁰ , and any of R ¹⁸¹ to R ¹⁹⁰ are used for bonding with L ¹ and for bonding with L ¹ The group is a single bond, and the X ¹ system is synonymous with X ¹ in the above general formula (2)]. An organic electroluminescence device according to claim 1 or 2, wherein b of the above general formula (1) is 1. For example, the organic electroluminescent element of claim 1 or 2, Wherein a of the above general formula (1) is 1 or 2. The organic electroluminescence device according to claim 1 or 2, wherein at least one of R ⁹ and R ¹⁰ of the above general formula (1) is a single bond for bonding with L ¹ . The organic electroluminescent device according to claim 1 or 2, wherein R ⁹ of the above general formula (1) is an aromatic hydrocarbon group selected from a substituted or unsubstituted ring-forming carbon number of 6 to 30, or substituted or An unsubstituted group forming a heterocyclic group having 5 to 30 atomic number of the ring. An organic electroluminescence device according to claim 1 or 2, wherein X ¹ and X ² are oxygen atoms. An organic electroluminescence device according to claim 3, wherein in the general formulas (8) to (10), any one of R ¹⁶¹ to R ¹⁶⁴ , any of R ¹⁷¹ to R ¹⁷⁴ , and R ¹⁸¹ to R ¹⁸⁴ Either one for bonding with L ¹ and a group for bonding with L ¹ is a single bond. The organic electroluminescence device according to claim 10, wherein the anthracene derivative represented by the above general formula (1) is represented by any one of the following general formulas (15) to (20). [R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (15) to (20) are each synonymous with R ¹ to R ⁸ in the above general formula ( ¹ ), and the X ¹ series in the above general formulas (15) to (20) It is synonymous with X ¹ in the above general formula (2)]. The organic electroluminescence device according to claim 10, wherein the anthracene derivative represented by the above general formula (1) is represented by any one of the following general formulas (51) to (56). [R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (51) to (56) are synonymous with R ¹ to R ⁸ in the above general formula ( ¹ ), and the X ¹ series in the above general formulas (51) to (56) It is synonymous with X ¹ in the above general formula (2)]. The organic electroluminescence device according to claim 10, wherein the anthracene derivative represented by the above general formula (1) is represented by any one of the following general formulas (57) to (62). [R ¹⁶¹ to R ¹⁹⁰ in the above general formulas (57) to (62) are synonymous with R ¹ to R ⁸ in the above general formula ( ¹ ), and the X ¹ series in the above general formulas (57) to (62) It is synonymous with X ¹ in the above general formula (2)]. The organic electroluminescence device according to claim 1, wherein R ²⁰ to R ²⁹ of the above general formula (21) are a hydrogen atom. The organic electroluminescence device according to claim 2, wherein Ar ²¹ and Ar ²³ of the above general formula (41) are a heterocyclic group represented by the above general formula (42). The organic electroluminescence device according to claim 2, wherein R ²¹ to R ²⁸ of the above general formula (41) are a hydrogen atom. The organic electroluminescent device of claim 2, wherein R ²² and R ²⁶ of the above general formula (41) are a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. The alkylmercaptoalkyl group of 3 to 30, wherein R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ of the above general formula (41) are a hydrogen atom. An organic electroluminescence device according to claim 2, wherein X ²¹ of the above general formula (42) is an oxygen atom.