WO2018123924A1

WO2018123924A1 - Composition, material for organic electroluminescent element, composition film, organic electroluminescent element, and electronic device

Info

Publication number: WO2018123924A1
Application number: PCT/JP2017/046297
Authority: WO
Inventors: 河村　昌宏; 博之岩渕; 由美子水木; 均熊
Original assignee: 出光興産株式会社
Priority date: 2016-12-26
Filing date: 2017-12-25
Publication date: 2018-07-05
Also published as: JP2020061390A

Abstract

A composition in which two or more compounds are mixed, containing at least a first compound expressed by general formula (1) and a second compound expressed by general formula (2). In general formula (1), a total of six ring structures expressed in general formula (1a) are included in R¹ to R⁴, A¹, and A². In general formula (2), at least one of A³ and A⁴ is a substituent expressed by general formula (2a), and the other is a substituent expressed by general formula (2b).

Description

Composition, material for organic electroluminescence device, composition film, organic electroluminescence device, and electronic device

The present invention relates to a composition, a material for an organic electroluminescence element, a composition film, an organic electroluminescence element, and an electronic apparatus.

Patent Document 1 and Patent Document 2 use a biscarbazole derivative having a specific structure having a cyano group as a first host and a compound having both a carbazolyl group derivative structure and a nitrogen-containing heteroaromatic ring as a second host. Organic electroluminescent devices are described. According to this organic electroluminescence element, Patent Document 1 and Patent Document 2 describe a long life.

International Publication No. 2013/084885 International Publication No. 2013/145923

As in Patent Document 1 and Patent Document 2, when two materials (for example, a first host and a second host) are vapor-deposited from different vapor deposition sources, there is a problem that the manufacturing process of the organic electroluminescence element is complicated. . On the other hand, the lifetime of an organic electroluminescent element using one material (for example, only one of the first host and the second host) is shortened. Therefore, a technique for stably depositing two (or a plurality of) materials from one deposition source is desired.
In the combination of the first host and the second host described in Patent Document 1 and Patent Document 2, when the deposition is performed from one deposition source, the ratio of the first host and the second host included in the formed layer is not stable. There is a problem that the performance of the organic electroluminescence element is not stable.

An object of the present invention is to provide a composition capable of stably depositing a ratio of materials from one vapor deposition source while maintaining the performance of the organic electroluminescence element, and an organic electroluminescence element including the composition Providing a material for use, providing a composition film containing the composition, providing an organic electroluminescence device containing the composition, and providing an electronic device including the organic electroluminescence device. .

According to one embodiment of the present invention, a composition in which two or more kinds of compounds are mixed, at least the first compound represented by the following general formula (1) and the following general formula (2) is represented. Compositions containing a second compound are provided.

(In the general formula (1),
R ¹ to R ⁴ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
When a is 2 or more, the plurality of R ¹ are the same as or different from each other.
When b is 2 or more, the plurality of R ² are the same as or different from each other.
When c is 2 or more, the plurality of R ³ are the same as or different from each other.
When d is 2 or more, the plurality of R ⁴ are the same as or different from each other.
A ¹ and A ² are each independently
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 6 to 30 ring atoms.
However, a total of six ring structures represented by the following general formula (1a) are included in R ¹ to R ⁴ , A ¹ and A ² . )

(In the general formula (1a), X ¹ , X ² and X ³ each independently represent C R ^X or N. At least one of the six ring structures represented by the general formula (1a) In the ring structure, at least one of X ¹ , X ² and X ³ represents N. When the ring structures represented by the general formula (1a) are bonded to form a condensed ring, There are cases where it does not.
R ^X , R ^X1 , R ^X2 and R ^X3 are each independently
Single bond,
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
When a plurality of R ^x are present, the plurality of R ^X are the same as or different from each other.
At least one of R ^X1 , R ^X2 , R ^X3 and one or more R ^X is a single bond. )

(In the general formula (2), R ²¹ to R ²⁴ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 30 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3, or 4;
f is 0, 1, 2, or 3.
g is 0, 1, 2, or 3.
h is 0, 1, 2, 3, or 4.
When e is 2 or more, the plurality of R ²¹ are the same as or different from each other.
When f is 2 or more, the plurality of R ²² are the same as or different from each other.
When g is 2 or more, the plurality of R ²³ are the same as or different from each other.
When h is 2 or more, the plurality of R ²⁴ are the same as or different from each other.
At least one of A ³ and A ⁴ is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b). )

(In the general formula (2a), Ar represents a substituted or unsubstituted triphenylenylene group.)

(In the general formula (2b), X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ each independently represent CR ^Y or N. R ^Y represents
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R ^Y are the same as or different from each other. )

According to one aspect of the present invention, there is provided a material for an organic electroluminescence device comprising the composition according to one aspect of the present invention.

According to an aspect of the present invention, there is provided a composition film including the composition according to the above-described aspect of the present invention.

According to one aspect of the present invention, an anode, a cathode, and an organic layer included between the anode and the cathode, wherein the organic layer is a composition according to one aspect of the present invention described above. An organic electroluminescent device comprising:

According to one aspect of the present invention, there is provided an electronic device equipped with the organic electroluminescence element according to one aspect of the present invention described above.

According to one embodiment of the present invention, it is possible to provide a composition capable of stably depositing a ratio of materials from one deposition source while maintaining the performance of the organic electroluminescence device, and to provide an organic including the composition. Providing a material for an electroluminescent element, providing a composition film including the composition, providing an organic electroluminescent element including the composition, and providing an electronic device including the organic electroluminescent element be able to.

It is a figure which shows schematic structure of an example of the organic electroluminescent element which concerns on one Embodiment.

(Composition)
The composition according to this embodiment is a composition in which two or more compounds are mixed.
The composition according to this embodiment contains at least a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2).

The form of the composition according to the present embodiment is not particularly limited. Examples of the form of the composition according to this embodiment include solids, powders, solutions, and films. When the composition according to this embodiment is a solid, it may be formed into a pellet.

(First compound)
The first compound is represented by the following general formula (1).

In the present specification, “a total of six ring structures represented by the general formula (1a) are included in R ¹ to R ⁴ , A ¹ and A ² ” means R ¹ to R ^4. , A ¹ and A ² mean that six 6-membered rings represented by the general formula (1a) are contained. The six 6-membered rings represented by the general formula (1a) are the same as or different from each other.
In addition, when the ring structures represented by the general formula (1a) are bonded to form a condensed ring, R ¹ to R ⁴ , A including the number of 6-membered rings constituting the condensed ring are included. 6-membered ring means that it contains six in ¹ and a ^2. In this case, for example, when the ring structures represented by the general formula (1a) are bonded to form a condensed ring represented by the following general formula (1b), the condensed ring includes two 6-membered rings. It will be out.

(In the general formula (1b),
X ^A is CR ¹⁰¹ R ¹⁰² , NR ¹⁰³ , an oxygen atom, or a sulfur atom.
R ¹⁰¹ to R ¹⁰³ are each independently
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms.
Y ¹ to Y ⁸ each independently represent CR ^X or N;
R ^X is
Single bond,
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
When there are a plurality of R ^x , the plurality of R ^X are the same as or different from each other;
At least one of the plurality of R ^X is a single bond. )

It is preferable that the first compound is a compound represented by the following general formula (3).

(In the general formula (3),
R ¹ to R ⁶ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
i is 0, 1, 2, 3, or 4.
j is 0, 1, 2, 3, 4, or 5.
When a is 2 or more, the plurality of R ¹ are the same as or different from each other.
When b is 2 or more, the plurality of R ² are the same as or different from each other.
When c is 2 or more, the plurality of R ³ are the same as or different from each other.
When d is 2 or more, the plurality of R ⁴ are the same as or different from each other.
When i is 2 or more, the plurality of R ⁵ are the same as or different from each other.
When j is 2 or more, the plurality of R ⁶ are the same as or different from each other.
B ¹ represents a substituent represented by the following general formula (4) or the following general formula (5). )

(In the general formula (4) and the general formula (5),
X ¹ to X ^{3 each} represent CR ^Z or a nitrogen atom.
R ^Z is
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R ^Z are the same as or different from each other.
R ⁷ to R ⁹ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A cyano group is shown.
k is 0, 1, 2, 3, 4, or 5.
l is 0, 1, 2, 3, 4, or 5;
m is 0, 1, 2, 3, or 4.
When k is 2 or more, the plurality of R ⁷ are the same as or different from each other.
When l is 2 or more, the plurality of R ⁸ are the same as or different from each other.
When m is 2 or more, the plurality of R ⁹ are the same as or different from each other. )

It is preferable that the first compound is a compound represented by the following general formula (6).

(In the general formula (6),
R ¹ to R ⁶ and R ¹⁰ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
i is 0, 1, 2, or 3.
j is 0, 1, 2, 3, 4, or 5.
n is 0, 1, 2, 3, 4, or 5.
When a is 2 or more, the plurality of R ¹ are the same as or different from each other.
When b is 2 or more, the plurality of R ² are the same as or different from each other.
When c is 2 or more, the plurality of R ³ are the same as or different from each other.
When d is 2 or more, the plurality of R ⁴ are the same as or different from each other.
When i is 2 or more, the plurality of R ⁵ are the same as or different from each other.
When j is 2 or more, the plurality of R ⁶ are the same as or different from each other.
When n is 2 or more, the plurality of R ¹⁰ are the same as or different from each other.
B ² represents a substituent represented by the following general formula (7). )

(In the general formula (7),
X ¹ to X ^{3 each} represent CR ^Z or a nitrogen atom.
R ^Z is
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R ^Z are the same as or different from each other.
R ¹¹ and R ¹² are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
o is 0, 1, 2, 3, 4, or 5.
p is 0, 1, 2, 3, 4, or 5.
When o is 2 or more, the plurality of R ¹¹ are the same as or different from each other.
When p is 2 or more, the plurality of R ¹² are the same as or different from each other. )

X ¹ , X ² , and X ³ in at least any one of the six ring structures represented by the general formula (1a) are preferably nitrogen atoms.

Of the six ring structures represented by the general formula (1a), in one ring structure, X ¹ , X ² , and X ³ are nitrogen atoms, and in the five ring structures, X ¹ , X ² , And X ³ are preferably CR ^Z , and R ^Z has the same meaning as described above.

In the first compound, one of A ¹ and A ² includes five 6-membered rings represented by the general formula (1a), and the other includes a 6-membered ring represented by the general formula (1a). It is also preferable that one is included.
In the first compound, one of A ¹ and A ² includes four 6-membered rings represented by the general formula (1a), and the other is a 6-membered represented by the general formula (1a). It is also preferred that two rings are included.

In the first compound, a, b, c and d are preferably 0.
In the first compound, i and j are preferably 0.
In the first compound, k, l and m are preferably 0.
In the first compound, n, o and p are preferably 0.

In the first compound, a, b, c, d, k, l, m, n, o and p are preferably 0.

Examples of the first compound according to this embodiment are shown below. The first compound in the present invention is not limited to these specific examples.

(Second compound)
The second compound is represented by the following general formula (2).

It is preferable that the second compound is a compound represented by the following general formula (8).

(In the general formula (8), R ²¹ to R ²⁴ are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3, or 4;
f is 0, 1, 2, or 3.
g is 0, 1, 2, or 3.
h is 0, 1, 2, 3, or 4.
When e is 2 or more, the plurality of R ²¹ are the same as or different from each other.
When f is 2 or more, the plurality of R ²² are the same as or different from each other.
When g is 2 or more, the plurality of R ²³ are the same as or different from each other.
When h is 2 or more, the plurality of R ²⁴ are the same as or different from each other.
At least one of A ³ and A ⁴ is a substituent represented by the following general formula (2a), and the other is a substituent represented by (2b). )

In the second compound, X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are CR ^Y , and R ^Y is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms. , A substituted or unsubstituted ring-forming cycloalkyl group having 3 to 25 carbon atoms, a silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group, and a plurality of R ^Y are the same as each other Or different.

In the second compound, X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are preferably CR ^Y and ^RY is preferably a hydrogen atom.

In the second compound, Ar is preferably an unsubstituted divalent triphenylenylene group.

In the second compound, e, f, g and h are preferably 0.

Examples of the second compound according to this embodiment are shown below. The second compound in the present invention is not limited to these specific examples.

Since the composition of the present embodiment contains a combination of the first compound and the second compound, the composition of the present embodiment can be used while maintaining the performance of the organic electroluminescence device. It is possible to stably deposit the material ratio from the deposition source.

(Mixing ratio)
In one embodiment of the present invention, the blending ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine suitably the compounding ratio of a 1st compound and a 2nd compound according to the effect calculated | required from a composition. The compounding ratio (mass ratio) of the compound represented by the first compound: second compound is usually in the range of 1:99 to 99: 1, and preferably in the range of 10:90 to 90:10. 40:60 to 60:40 is more preferable.

(Materials for organic electroluminescence elements)
The material for an organic electroluminescence element according to this embodiment includes the composition according to this embodiment. That is, the organic electroluminescent element material according to the present embodiment contains the first compound and the second compound.
The material for an organic electroluminescence element according to this embodiment may further contain other compounds. When the organic electroluminescent element material according to the present embodiment further includes other compounds, the other compounds may be solid or liquid.

(Composition film)
The composition film according to the present embodiment includes the composition according to the present embodiment. That is, the film (composition film) containing the composition according to the present embodiment means a film containing the first compound and the second compound.
The composition film according to the present embodiment may further contain other compounds.
The method for forming the composition film according to the present embodiment is not particularly limited unless otherwise specified in the present specification. As a method for forming the composition film, known methods such as a dry film forming method and a wet film forming method can be employed. Examples of the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method. Examples of the wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.

(Element structure of organic EL element)
The organic EL element according to this embodiment includes an organic layer between a pair of electrodes. This organic layer includes at least one layer composed of an organic compound. Alternatively, the organic layer is formed by laminating a plurality of layers composed of organic compounds. The organic layer may further contain an inorganic compound. In the organic EL device of the present embodiment, at least one of the organic layers is a light emitting layer. Therefore, the organic layer may be composed of, for example, a single light emitting layer or may include a layer that can be employed in an organic EL element. The layer that can be employed in the organic EL element is not particularly limited. For example, at least one selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a barrier layer. Layer.

In this embodiment, the organic layer is preferably composed of a plurality of layers, and the composition according to this embodiment is preferably contained in one or more of the plurality of layers.

By using the composition according to this embodiment in any one or more layers of the organic EL element according to this embodiment, high organic EL performance (for example, light emission performance of at least one of driving voltage, light emission efficiency, and lifetime) ) Can be obtained. Further, when the composition according to the present embodiment is formed using the method according to the present embodiment (for example, vacuum deposition method), the first compound and the second compound in the light emitting layer from the initial deposition stage to the final deposition stage. The material ratio with the compound is stable. As a result, the organic EL element can stably maintain high light emission performance regardless of the deposition time.
In the organic EL device according to this embodiment, the light emitting layer preferably contains the composition according to this embodiment.

In this embodiment, it is preferable that a hole transport layer is further provided between the anode and the light emitting layer.
In this embodiment, it is preferable to further have an electron transport layer between the cathode and the light emitting layer.
As another embodiment, it is also preferable that the composition according to an embodiment of the present invention is used in the electron transport zone.

As typical element configurations of the organic EL element, for example, the following configurations (a) to (f) can be given.
(A) Anode / light emitting layer / cathode (b) Anode / hole injection / transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron injection / transport layer / cathode (d) Anode / hole injection / transport Layer / light emitting layer / electron injection / transport layer / cathode (e) anode / hole injection / transport layer / light emitting layer / barrier layer / electron injection / transport layer / cathode (f) anode / hole injection / transport layer / barrier Layer / light emitting layer / barrier layer / electron injection / transport layer / cathode Among the above, the structure of (d) is preferably used. However, the present invention is not limited to these configurations. The “light emitting layer” is an organic layer having a light emitting function. The “hole injection / transport layer” means “at least one of a hole injection layer and a hole transport layer”. The “electron injection / transport layer” means “at least one of an electron injection layer and an electron transport layer”. When the organic EL element has a hole injection layer and a hole transport layer, it is preferable that a hole injection layer is provided between the hole transport layer and the anode. Moreover, when an organic EL element has an electron injection layer and an electron carrying layer, it is preferable that the electron injection layer is provided between the electron carrying layer and the cathode. In addition, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be composed of a single layer or a plurality of layers.

FIG. 1 shows a schematic configuration of an example of the organic EL element according to this embodiment.
The organic EL element 1 includes a translucent 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 includes a hole injection layer 6, a hole transport layer 7, a light emitting layer 5, an electron transport layer 8, and an electron injection layer 9. In the organic layer 10, a hole injection layer 6, a hole transport layer 7, a light emitting layer 5, an electron transport layer 8, and an electron injection layer 9 are laminated in this order from the anode 3 side.

(Light emitting layer)
The light emitting layer 5 of the organic EL element 1 contains the composition according to the present embodiment. That is, the light emitting layer 5 includes the first compound and the second compound.

According to the organic EL device of the present embodiment, the organic EL device is driven at a low voltage by using the first compound and the second compound in combination in the organic layer. From the viewpoint of driving the organic EL element at a low voltage, an embodiment in which the first compound and the second compound are contained in one light emitting layer is preferable.

In the organic EL device of the present embodiment, the ratio of the total mass of the first compound and the second compound contained in the organic layer is preferably 1% by mass or more and 100% by mass or less.

(Mixing ratio)
In one embodiment of the present invention, the blending ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine suitably the compounding ratio of a 1st compound and a 2nd compound according to the effect calculated | required from an organic EL element. The compounding ratio (mass ratio) of the compound represented by the first compound: second compound is usually in the range of 1:99 to 99: 1, and preferably in the range of 10:90 to 90:10. 40:60 to 60:40 is more preferable.

(Luminescent material)
In the organic EL element which is one embodiment of the present invention, the light emitting layer preferably further contains a light emitting material.
In one embodiment of the present invention, it is preferable that the light emitting layer contains a phosphorescent material as a light emitting material. The phosphorescent material is preferably an orthometalated complex of any metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt). Suitable phosphorescent materials will be described later.

When the light emitting layer includes the first compound, the second compound, and the light emitting material, the content of the light emitting material in the light emitting layer is preferably 0.1% by mass or more and 50% by mass or less. % To 20% by mass is more preferable.

(Layer formation method)
The formation method of each layer of the organic EL element which is one embodiment of the present invention is not particularly limited unless otherwise specified in the present specification. As a method for forming each layer, known methods such as a dry film forming method and a wet film forming method can be employed. Examples of the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method. Examples of the wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.

(Film thickness)
The film thickness of each layer of the organic EL element which is one embodiment of the present invention is not limited except as specifically mentioned above. The film thickness of each layer needs to be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, and the efficiency may deteriorate. If the film thickness is too thin, pinholes and the like are generated, and there is a possibility that sufficient light emission luminance cannot be obtained even when an electric field is applied. Usually, the film thickness is suitably in the range of 5 nm to 10 μm, more preferably in the range of 10 nm to 0.2 μm.

Hereinafter, materials of constituent elements of the organic EL element will be described.
(substrate)
The substrate is used as a support for the light emitting element. As the substrate, for example, glass, quartz, plastic, or the like can be used. Further, a flexible substrate may be used. The flexible substrate is a substrate that can be bent (flexible), and examples thereof include a plastic substrate made of polycarbonate or polyvinyl chloride.

(anode)
For the anode formed on the substrate, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more). Specifically, for example, indium tin oxide (ITO), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, and indium oxide containing zinc oxide. And graphene. In addition, gold (Au), platinum (Pt), a nitride of a metal material (for example, titanium nitride), or the like can be given.

(Hole injection layer)
The hole injection layer is a layer provided for efficiently injecting holes from the anode into the organic layer. Substances used for the hole injection layer include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide An oxide, a tungsten oxide, a manganese oxide, an aromatic amine compound, an acceptor compound, a polymer compound (oligomer, dendrimer, polymer, etc.), or the like can also be used.
Among them, the substance used for the hole injection layer is preferably an aromatic amine derivative or an acceptor compound, and more preferably an acceptor compound. As the acceptor compound, a heterocyclic derivative substituted with an electron withdrawing group, a quinone derivative substituted with an electron withdrawing group, an arylborane derivative, a heteroarylborane derivative, or the like is preferably used. Among them, hexacyanohexaazatriphenylene, F ₄ TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or 1,2,3-tris [(cyano) (4-cyano-2,3 , 5,6-tetrafluorophenyl) methylene] cyclopropane and the like are preferably used.
The layer containing an acceptor compound is preferably in a form further containing a matrix material. A wide variety of materials for organic EL can be used as the matrix material. As the matrix material used together with the acceptor compound, a donor compound is preferably used, and an aromatic amine compound is more preferably used.

(Hole transport layer)
The hole transport layer is a layer containing a substance having a high hole transport property. An aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used for the hole transport layer. A high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used. Note that other than these substances, any substance that has a property of transporting more holes than electrons may be used. Note that the layer containing a substance having a high hole-transport property is not limited to a single layer, and two or more layers containing the above substances may be stacked. The hole transport material is preferably a compound represented by the following general formula (H).

In the general formula (H), Ar ₁ to Ar ₃ are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms. Or a group composed of a combination of a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a triphenylenyl group and the like are preferable. As the heterocyclic group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group and the like are preferable. As a group composed of a combination of an aryl group and a heterocyclic group, a dibenzofuran-substituted aryl group, a dibenzothiophene-substituted aryl group, a carbazole-substituted aryl group, and the like are preferable. These substituents may further have a substituent, and preferred substituents are as described below.
As a preferred embodiment, at least one of Ar ₁ to Ar _{3 in} the general formula (H) is preferably a compound further substituted with an arylamino group, and is a diamine derivative, a triamine derivative, or a tetraamine derivative. It is also preferable. Examples of diamine derivatives include tetraaryl-substituted benzidine derivatives and TPTE (4,4′-bis [N-phenyl-N- [4′-diphenylamino-1,1′-biphenyl-4-yl] amino] -1,1 '-Biphenyl] and the like are preferably used.
The hole transporting material used for the layer in contact with the phosphorescent light emitting layer preferably has a high triplet level, and Ar ₁ to Ar ₃ in the general formula (H) are fluorenyl group, spirofluorenyl group, phenyl group. And a group formed by a substituent such as a biphenyl group, a phenanthryl group, a triphenylenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a combination thereof.

(Light emitting layer)
The light-emitting layer is a layer including a substance having high light-emitting properties, and various materials can be used. The light emitting layer usually contains a light emitting material (dopant material) having a high light emitting property and a host material for efficiently emitting light. For example, as the substance having high light-emitting property, a fluorescent compound that emits fluorescence or a phosphorescent compound that emits phosphorescence can be used. A fluorescent compound is a compound that can emit light from a singlet excited state, and a phosphorescent compound is a compound that can emit light from a triplet excited state. The light emitting layer containing a fluorescent compound is called a fluorescent light emitting layer, and the light emitting layer containing a phosphorescent compound is called a phosphorescent light emitting layer.

Fluorescent compounds can be widely used as dopant materials for the fluorescent layer. As the dopant material for the fluorescent light emitting layer, among them, condensed polycyclic aromatic derivatives, styrylamine derivatives, condensed ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like are preferable. More preferable examples of the dopant material for the fluorescent light emitting layer include condensed ring amine derivatives and boron-containing compounds. Examples of the condensed ring amine derivative include diaminopyrene derivatives, diaminochrysene derivatives, diaminoanthracene derivatives, diaminofluorene derivatives, and diaminofluorene derivatives in which one or more benzofuro skeletons are condensed. Examples of the boron-containing compound include a pyromethene derivative and a triphenylborane derivative. Here, the term “derivative” refers to a compound that includes the skeleton as a partial structure, and includes a compound that forms a further condensed ring and a compound that forms a ring between substituents. For example, in the case of a condensed polycyclic aromatic derivative, it is a compound that contains a condensed polycyclic aromatic skeleton as a partial structure, a compound that further forms a condensed ring in the condensed polycyclic aromatic skeleton, and the condensed polycyclic aromatic Also included are compounds that form a ring with substituents of the skeleton.

A general fluorescent material can be used as a host material used for the fluorescent light emitting layer. The host material used for the fluorescent light-emitting layer is preferably a compound having a condensed polycyclic aromatic derivative as a main skeleton, and particularly preferably an anthracene derivative, a pyrene derivative, a chrysene derivative, or a naphthacene derivative. . A host particularly suitable as a blue host material (a host material used with a blue fluorescent light-emitting dopant material) and a green host material (a host material used with a green fluorescent light-emitting dopant material) is represented by the following general formula (X). It is an anthracene derivative represented.

In the general formula (X), Ar _X1 and Ar _X2 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring atom having 3 to 50 ring atoms. A heterocyclic group is shown. Ar _X1 and Ar _X2 each independently preferably represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a heterocyclic group having 5 to 30 ring atoms.

As a phosphorescent material (dopant material) that can be used for the phosphorescent layer, a metal complex such as an iridium complex, an osmium complex, or a platinum complex is used.
The phosphorescent material that is an orthometalated complex of a metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt) is a complex represented by the following formula (α). preferable.

In the formula (α), M represents at least one metal selected from the group consisting of osmium, iridium and platinum, and n represents the valence of the metal.
Ring A ₁ represents a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a heteroaryl group having 5 to 30 ring atoms, and Ring A ₂ is a substituted group containing nitrogen as a hetero ring forming atom. Alternatively, it represents an unsubstituted heteroaryl group having 5 to 30 ring atoms.

Examples of the aryl group having 6 to 24 ring carbon atoms in the ring A ₁ of the formula (α) include the aryl groups in the general formula (1) described above.
Examples of the heteroaryl group having 5 to 30 ring atoms in the ring A ₁ and the ring A ₂ of the formula (α) include the heteroaryl groups in the general formula (1) described above.
The substituent that the ring A ₁ and the ring A _{2 of the} formula (α) may have is the same as the substituent in the general formula (1) described above.
Furthermore, the complex represented by the formula (α) is preferably a complex represented by the following formula (T) or (U).

In formula (T), M represents a metal, and ring B and ring C each independently represent an aryl group or heteroaryl group having 5 or 6 ring atoms.
Ring A-ring B represents a bond pair of an aryl group or a heteroaryl group, and is coordinated to the metal M through the nitrogen atom of ring A and the sp ² hybrid atom of ring B.
Ring A to ring C represent a bond pair of an aryl group or a heteroaryl group.
R _a , R _b and R _c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted group; Amino group, substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted This represents any one selected from the group consisting of an aryl group having 6 to 24 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, and R _a is 1 or more and 4 or less R _b is 1 or more and 4 or less, R _c is 1 or more and 4 or less, and the numbers of R _a , R _b and R _c are independent of each other.
X ₁ to X ₉ each independently represents a carbon atom or a nitrogen atom.
R _d and R _e are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted amino group, Substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted ring-forming carbon R _c , R _d and R _e bonded to the ring C, each represented by any one selected from the group consisting of an aryl group having 6 to 24 and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms At least one of is not a hydrogen atom.
m represents an oxidation state of the metal M, and n is 1 or more. L ′ represents a monoanionic bidentate ligand.

In the formula (T), examples of M include osmium, iridium, and platinum, and iridium is particularly preferable.
Examples of the aryl group having 5 or 6 ring atoms represented by ring B and ring C include the aryl group in the general formula (1) described above.
Examples of the heteroaryl group having 5 or 6 ring atoms represented by ring B and ring C include the heteroaryl group in the general formula (1) described above.
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms represented by R ₁ , R ₂ , R _a , R _b and R _c , a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, substituted or unsubstituted The aralkyl group having 7 to 50 carbon atoms, the substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms and the substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms are as described above. The same group is mentioned.
As the substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms and the substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms represented by R ₁ , R ₂ , R _a , R _b and R _c , respectively, And the same groups as described above.
Examples of the monoanionic bidentate ligand represented by L ′ include a ligand represented by the following formula (L ′).

In the formula _{_{(L '), X 4 ~}} X 9, R a, and _{R b} are the same as _{_{_{X 4 ~ X 9, R a}}} , and _{R b} in Formula (T), preferable embodiments thereof are also the same.
The ligand represented by the formula (L ′) is represented by the formula (T) through a solid line extending from the ring X ₉ to the outside of the ring B and a broken line extending from the nitrogen atom of the ring A to the outside of the ring A. Coordinates to metal M.

In the formula (U), X represents any one selected from the group consisting of NR, oxygen atom, sulfur atom, BR, and selenium atom, and R represents a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 25 It is an alkyl group.
R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms. R ₁ is 1 or more and 4 or less, R ₂ is 1 or more and 4 or less, and R ₃ is 1 or more and 4 or less , R ₄ is 1 or more and 4 or less, and the numbers of R ₁ , R ₂ , R ₃ and R ₄ are independent of each other.

In the formula (U), examples of the alkyl group having 1 to 25 carbon atoms represented by R, R ₁ , R ₂ , R ₃ and R ₄ include the groups described above, and preferred embodiments thereof are also the same.
In addition, examples of the aryl group having 6 to 24 ring carbon atoms represented by R ₁ , R ₂ , R _3, and R ₄ include the groups described above, and preferred embodiments thereof are also the same.

As the complex represented by the formula (T) or (U), the following compounds are suitable, but are not particularly limited thereto.

Further, as the phosphorescent material, an iridium complex represented by the following formula (β) is also preferable.

In the formula (β), A ¹ to A ⁸ contain a carbon atom or a nitrogen atom, at least one of A ¹ to A ⁸ is a nitrogen atom, ring B is bonded to ring A by a C—C bond, and iridium (Ir) is bonded to ring A through an Ir—C bond.
In the formula (β), it is preferred that only one of A ¹ to A ⁸ is a nitrogen atom, more preferred that only one of A ⁵ to A ⁸ is a nitrogen atom, and A ⁵ is A nitrogen atom is preferred. In the formula (β), it is preferable that A ³ and A ⁴ are carbon atoms among A ¹ to A ⁴ . In the formula (β), A ⁵ is preferably a nitrogen atom, and A ¹ to A ⁴ and A ⁶ to A ⁸ are preferably carbon atoms.
A ⁶ is preferably CR (carbon atom to which R is bonded), and R is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms. , And combinations thereof. R is preferably a substituted or unsubstituted alkyl having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl having 3 to 25 ring carbon atoms.
In the formula (β), X is O, S or Se, and O is preferable.
In the formula (β), R ¹ to R ⁴ are each independently mono-substituted, di-substituted, tri-substituted or tetra-substituted, or unsubstituted, and adjacent R ¹ to R ⁴ are bonded to each other. To form a ring, and R ¹ to R ⁴ are each independently
hydrogen,
deuterium,
halogen,
Substituted or unsubstituted alkyl having 1 to 25 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 25 ring carbon atoms,
Substituted or unsubstituted heteroalkyl having 2 to 25 atoms,
Substituted or unsubstituted arylalkyl having 7 to 50 carbon atoms,
Substituted or unsubstituted alkoxy having 1 to 25 carbon atoms,
Substituted or unsubstituted aryloxy having 6 to 24 ring carbon atoms,
Substituted or unsubstituted amino,
Substituted silyl,
Substituted or unsubstituted alkenyl having 2 to 25 carbon atoms,
Cycloalkenyl having 3 to 25 ring carbon atoms,
Heteroalkenyl having 3 to 25 atoms,
Alkynyl having 2 to 25 carbon atoms,
Aryl having 6 to 24 ring carbon atoms,
Heteroaryl having 5 to 30 ring atoms,
Acyl,
Substituted carbonyls,
carboxylic acid,
ester,
Nitrile,
Isonitrile,
Sulfanyl,
Sulfinyl,
Sulfonyl,
Selected from the group consisting of phosphino and combinations thereof, the substituted silyl is substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 25 carbon atoms and aryl groups having 6 to 24 ring carbon atoms. The substituted carbonyl is a carbonyl substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms. In the formula (β), R ¹ to R ⁴ are preferably each independently selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 25 carbon atoms, and combinations thereof. At least one of R ² and R ³ is preferably an alkyl group having 1 to 25 carbon atoms, more preferably the alkyl group is deuterated or partially deuterated.
In the formula (β), n is an integer of 1 to 3, and is preferably 1.

Specific examples of the iridium complex represented by the formula (β) are shown below, but are not limited thereto.

As the complex represented by the formula (α), in addition to the complex represented by the formula (T) or (U), the complex represented by the following formula (V), (X), (Y) or (Z) It can also be used.

In the formula (V), (X), (Y) or (Z), R ⁵⁰ to R ⁵⁴ are each independently a hydrogen atom or a substituent, k is an integer of 1 to 4, and 1 is 1 Is an integer from 4 to 4, and m is an integer from 1 to 2. M is Ir, Os, or Pt.
^Examples of the substituent represented by R ⁵⁰ to R ⁵⁴ are the same as those described above.
Formula (V) is preferably represented by the following formula (V-1), and formula (X) is preferably represented by the following formula (X-1) or formula (X-2). In the following formulas (V-1), (X-1), and (X-2), R ⁵⁰ , k, and M are the same as R ⁵⁰ , k, and M described above.

Specific examples of the complex represented by the formula (V), (X), (Y) or (Z) are shown below, but are not particularly limited thereto.

(Host material for light emitting layer)
The host material used for the phosphorescent light-emitting layer is preferably a material having a triplet level higher than that of the phosphorescent dopant, and a phosphorescent host material such as a general aromatic derivative, heterocyclic derivative, or metal complex is used. Can do. Among the host materials used for the phosphorescent light emitting layer, aromatic derivatives and heterocyclic derivatives are preferable, and examples of aromatic derivatives include naphthalene derivatives, triphenylene derivatives, phenanthrene derivatives, and fluoranthene derivatives. Examples include indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, and dibenzothienyl derivatives. Here, the derivative is defined as described above.
One preferred form of the host material used for the phosphorescent light emitting layer is a composition according to an embodiment of the present invention.

(Electron transport layer)
The electron transport layer is a layer containing a substance having a high electron transport property.
In order to improve the performance of the organic EL element, one or more layers may be provided between the electron transport layer and the light emitting layer. This layer is called a second electron transport layer, a hole blocking layer, a triplet block layer, or the like. In order to improve the hole barrier property, it is preferable to use a material having a deep HOMO level. In order to improve the triplet blocking property, it is preferable to use a material having a high triplet level.
The electron transport layer includes metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, heterocyclic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, condensed aromatic hydrocarbon derivatives, and Polymeric compounds can be used. Preferably, imidazole derivatives (for example, benzimidazole derivatives, imidazopyridine derivatives, benzimidazophenanthridine derivatives), azine derivatives (for example, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, phenanthroline derivatives, etc., and these heterocyclic rings Phosphine oxide-based substituents), and aromatic hydrocarbon derivatives (for example, anthracene derivatives and fluoranthene derivatives).
As one preferred form of the material contained in the electron transport layer, hole blocking layer, or triplet block layer, the composition according to one embodiment of the present invention can be used.
As one preferable mode, the electron transport layer is formed of an alkali metal derivative (for example, lithium quinolinate complex) such as an alkali metal (Li, Cs, etc.), an alkaline earth metal (Mg, etc.), and an alloy containing these. And at least one selected from the group consisting of alkaline earth metal derivatives. When the electron transport layer contains at least one of alkali metals, alkaline earth metals and alloys thereof, the content ratio in the electron transport layer is preferably 0.1 to 50% by mass, more preferably 0.1 to 20%. % By mass, more preferably 1 to 10% by mass, and when the electron transport layer contains at least one of an alkali metal derivative and an alkaline earth metal derivative, the content ratio in the electron transport layer is preferably It is 1 to 99% by mass, more preferably 10 to 90% by mass.

(Electron injection layer)
The electron injection layer is a layer containing a substance having a high electron injection property. For the electron injection layer, alkali metals such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), lithium oxide (LiO _x ), and the like are used. Alkali metal derivatives (for example, lithium quinolinate complexes) and alkaline earth metal derivatives such as metals or alloys containing them can be used.

(cathode)
For the cathode, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less). Specific examples of such cathode materials include elements belonging to Group 1 or Group 2 of the Periodic Table of Elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and alkaline earth such as magnesium (Mg). And other rare earth metals such as alloys, alloys containing them (for example, MgAg, AlLi), and alloys containing these.

In this specification, the hydrogen atom includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (triuterium), and tritium.

In this specification, the number of ring-forming carbon atoms constitutes the ring itself of a compound having a structure in which atoms are bonded cyclically (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, or a heterocyclic compound). Represents the number of carbon atoms in the atom. When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons. The “ring-forming carbon number” described below is the same unless otherwise specified. For example, the benzene ring has 6 ring carbon atoms, the naphthalene ring has 10 ring carbon atoms, the pyridinyl group has 5 ring carbon atoms, and the furanyl group has 4 ring carbon atoms. Further, when an alkyl group is substituted as a substituent on the benzene ring or naphthalene ring, the carbon number of the alkyl group is not included in the number of ring-forming carbons. In addition, for example, when a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the carbon number of the fluorene ring as a substituent is not included in the number of ring-forming carbons.

In the present specification, the number of ring-forming atoms means a compound (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocycle) having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic ring, a condensed ring, or a ring assembly). Of the ring compound) represents the number of atoms constituting the ring itself. Atoms that do not constitute a ring or atoms included in a substituent when the ring is substituted by a substituent are not included in the number of ring-forming atoms. The “number of ring-forming atoms” described below is the same unless otherwise specified. For example, the pyridine ring has 6 ring atoms, the quinazoline ring has 10 ring atoms, and the furan ring has 5 ring atoms. A hydrogen atom bonded to a carbon atom of a pyridine ring or a quinazoline ring or an atom constituting a substituent is not included in the number of ring-forming atoms. Further, when, for example, a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.

In the present specification, the “carbon number XX to YY” in the expression “substituted or unsubstituted ZZ group having XX to YY” represents the number of carbon atoms in the case where the ZZ group is unsubstituted. The carbon number of the substituent in the case where it is present is not included.

In this specification, “atom number XX to YY” in the expression “a ZZ group having a substituted or unsubstituted atom number XX to YY” represents the number of atoms when the ZZ group is unsubstituted. In this case, the number of substituent atoms is not included.

In this specification, “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the above substituent.

Specific examples of each group in the formulas in this specification and the substituents in the above description of “substituted or unsubstituted” will be described.

Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl (including isomeric groups), hexyl Groups (including isomer groups), heptyl groups (including isomer groups), octyl groups (including isomer groups), nonyl groups (including isomer groups), decyl groups (including isomer groups), undecyl Groups (including isomer groups), dodecyl groups (including isomer groups), and the like. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a pentyl group (all including an isomer group) are preferable. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group are more preferable, and methyl group, ethyl group, isopropyl group and t-butyl group are particularly preferable. preferable.

The carbon number of the alkyl group is 1 to 25, preferably 1 to 10.

Examples of the halogenated alkyl group in which the alkyl group is substituted with a halogen atom include groups in which the alkyl group having 1 to 25 carbon atoms is substituted with one or more halogen atoms, preferably a fluorine atom.
Specific examples of the halogenated alkyl group having 1 to 25 carbon atoms in the present specification include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoromethylmethyl group, a trifluoroethyl group, A pentafluoroethyl group etc. are mentioned.

The alkenyl group is a group having a double bond in the alkyl group, and the alkenyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferably, it is a vinyl group.

The alkynyl group is a group having a triple bond in the alkyl group, and the alkynyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferred is an ethynyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
The number of carbon atoms forming the ring of the cycloalkyl group is 3 to 25, preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.

The alkoxy group is a group represented by —OY ¹⁰ , and examples of Y ¹⁰ include the same groups as those described above for the alkyl group and the cycloalkyl group. The number of carbon atoms of the alkoxy group is preferably 1 to 25, more preferably 1 to 10.

The alkylthio group is a group represented by —SY ¹⁰ , and examples of Y ¹⁰ include the same groups as those described above for the alkyl group and the cycloalkyl group.
The alkylthio group has 1 to 25 carbon atoms, preferably 1 to 10 carbon atoms.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably a fluorine atom.

Examples of aryl groups include phenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c] phenanthryl, phenalenyl, fluorenyl, Picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl group, benzo [b ] A triphenylenyl group, a perylenyl group, etc. are mentioned. Among these, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluoranthenyl group, and a fluorenyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is more preferable.
The aryl group has 6-30 ring-forming carbon atoms, preferably 6-24, more preferably 6-20, and even more preferably 6-18.

The arylene group is a divalent group Y ²¹ in which one hydrogen atom or substituent is further removed from the aryl group.

The aralkyl group is represented as —Y ¹¹ —Y ²⁰ . An example of Y ¹¹ is a divalent group (an alkylene group or a cycloalkylene group) obtained by further removing one hydrogen atom or substituent from those exemplified as the alkyl group and the cycloalkyl group. Examples of Y ²⁰ include the aryl group.

The aryloxy group is represented as —OY ²⁰ and examples of Y ²⁰ include the same as those mentioned as the aryl group.
The heteroaryloxy group is represented as —OY ^30, and examples of Y ³⁰ include the same as those described below as the heteroaryl group.

The arylthio group is represented by —SY ^20, and examples of Y ²⁰ include the same as those mentioned as the aryl group.
The heteroarylthio group is represented by —SY ^30, and examples of Y ³⁰ include the same groups as those described below as the heteroaryl group.

The arylcarbonyloxy group is represented by —O— (C═O) —Y ^20, and examples of Y ²⁰ include the same as those mentioned as the aryl group.

A substituted carbonyl group having a substituent selected from an alkyl group and an aryl group is represented by — (C═O) —Y ¹⁰ or — (C═O) —Y ^20, and examples of Y ¹⁰ include the alkyl group And the same as those mentioned as the cycloalkyl group, and examples of Y ²⁰ include the same as those mentioned as the aryl group.

The heterocyclic group includes a heterocyclic group having no aromaticity and an aromatic heterocyclic group having aromaticity (a monoaryl is a heteroaryl group, and a bivalent is a heteroarylene group).

Examples of the heterocyclic group having no aromaticity include a ring group having 3 to 30, preferably 3 to 20 ring-forming atoms including a nitrogen atom, an oxygen atom or a sulfur atom. Specific examples of the heterocyclic ring having no aromaticity include aziridine, oxirane, thiirane, azetidine, oxetane, trimethylene sulfide, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, tetrahydrothiopyran and the like.

Examples of the heterocyclic group include a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a sulfur atom, and the ring-forming atom is selected from the group consisting of a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable to contain the atoms. As the heterocyclic group, a heteroaryl group having aromaticity is preferable. Examples of heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, imidazopyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl , Isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothiophenyl group, isobenzothiophenyl group, indolizinyl group, quinolidinyl group, quinolyl group , Isoquinolyl group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimidazolyl group, benzoxazolyl group, benzthiazolyl group, indazolyl group, benzisoxyl group Ryl, benzisothiazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9-phenylcarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl Group, phenoxazinyl group and xanthenyl group. Among these, pyridyl group, imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, aryl group or heterocyclic group at the 9-position A substituted carbazolyl group, phenanthrolinyl group and quinazolinyl group are preferred.

The number of ring-forming atoms of the heterocyclic group is from 3 to 30, preferably from 5 to 24, more preferably from 5 to 18.
The number of ring-forming atoms of the heteroaryl group is 5 to 30, preferably 5 to 24, more preferably 5 to 18.
The ring-forming atom other than the carbon atom of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

The heteroarylene group is a divalent group Y ³¹ in which one hydrogen atom or substituent is further removed from the heteroaryl group.

In the present specification, the heterocyclic group may be a group derived from a partial structure represented by the following general formulas (XY-1) to (XY-18), for example.

In the general formulas (XY-1) to (XY-18), X _A and Y _A are each independently a hetero atom, and an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, or a germanium atom Is preferred. The partial structures represented by the general formulas (XY-1) to (XY-18) have a bond at an arbitrary position to be a heterocyclic group, and this heterocyclic group has a substituent. Also good.

In addition, in the present specification, the substituted or unsubstituted carbazolyl group may include a group further condensed with a carbazole ring as represented by the following formula, for example. Such a group may also have a substituent. Also, the position of the joint can be changed as appropriate.

The mono-substituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —NH (Y ¹⁰ ) or —NH (Y ²⁰ ), and Y ¹⁰ and Y ²⁰ are as described above.
The disubstituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —N (Y ¹⁰ ) ₂ , —N (Y ²⁰ ) ₂ or —N (Y ¹⁰ ) (Y ²⁰ ), and Y ¹⁰ And Y ²⁰ are as described above. When two Y ¹⁰ or Y ²⁰ are present, they may be the same as or different from each other.

The mono-substituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH ₂ (Y ¹⁰ ) or —SiH ₂ (Y ²⁰ ).
The disubstituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH (Y ¹⁰ ) ₂ , —SiH (Y ²⁰ ) ₂ or —SiH (Y ¹⁰ ) (Y ²⁰ ).
The tri-substituted silyl group having a substituent selected from an alkyl group and an aryl group is -Si (Y ¹⁰ ) ₃ , -Si (Y ²⁰ ) ₃ , -Si (Y ¹⁰ ) ₂ (Y ²⁰ ) or -Si (Y ¹⁰ ) (Y ²⁰ ) ₂ . Y ¹⁰ and Y ²⁰ are as described above, and when there are a plurality of Y ¹⁰ or Y ^{20 s} , they may be the same as or different from each other.

The substituted sulfonyl group having a substituent selected from an alkyl group and an aryl group is represented by —S (═O) ₂ —Y ¹⁰ or —S (═O) ₂ —Y ²⁰ , and Y ¹⁰ and Y ²⁰ are the above-mentioned Street.

The di-substituted phosphoryl group having a substituent selected from an alkyl group and an aryl group is -OP (= O) (Y ¹⁰ ) ₂ , -OP (= O) (Y ²⁰ ) ₂ or -OP (= O) (Y ¹⁰ ) (Y ²⁰ ) Y ¹⁰ and Y ²⁰ are as described above, and when two Y ¹⁰ or Y ²⁰ are present, they may be the same as or different from each other.

The alkylsulfonyloxy group having an alkyl group is represented by —O—S (═O) ₂ (Y ¹⁰ ), and Y ¹⁰ is as described above.

The arylsulfonyloxy group having a substituent selected from an aryl group is represented by —O—S (═O) ₂ (Y ²⁰ ), and Y ²⁰ is as described above.

In this specification, the substituent in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, and an alkyl group having 1 to 25 carbon atoms. Group (straight chain or branched alkyl group), cycloalkyl group having 3 to 25 ring carbon atoms, halogenated alkyl group having 1 to 25 carbon atoms, alkylsilyl group having 3 to 25 carbon atoms, ring carbon number 6 An arylsilyl group having 30 to 30 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, a heteroaryloxy group having 5 to 30 ring atoms, a substituted amino group, 1 to 25 carbon atoms Alkylthio group, arylthio group having 6 to 30 ring carbon atoms, heteroarylthio group having 5 to 30 ring atoms, aralkyl group having 7 to 30 carbon atoms, heteroaryl having 5 to 30 carbon atoms Is substituted with an alkyl group substituted with, an alkenyl group with 2 to 30 carbon atoms, an alkynyl group with 2 to 30 carbon atoms, an aryl group with 6 to 30 ring carbon atoms or a heterocyclic group with 5 to 30 ring atoms. A phosphoryl group, an aryl group having 6 to 30 ring carbon atoms, or a boryl group substituted with a heterocyclic group having 5 to 30 ring atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, and a carboxy group. There may be mentioned at least one group selected from the group.

In this specification, the substituent in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, and an alkyl group having 1 to 25 carbon atoms. Preferred is at least one group selected from the group consisting of a group (straight chain or branched alkyl group), an alkylsilyl group having 3 to 25 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, and a cyano group. Furthermore, specific substituents that are preferable in the description of each substituent are preferable.

In the present specification, the substituent in the case of “substituted or unsubstituted” is an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, or an alkyl group having 1 to 25 carbon atoms. (Straight chain or branched chain alkyl group), cycloalkyl group having 3 to 25 ring carbon atoms, alkylsilyl group having 3 to 25 carbon atoms, arylsilyl group having 6 to 30 ring carbon atoms, 1 to 25 carbon atoms Alkoxy groups having 5 to 30 ring carbon atoms, substituted amino groups, alkylthio groups having 1 to 25 carbon atoms, arylthio groups having 6 to 30 ring carbon atoms, aralkyl groups having 7 to 30 carbon atoms, carbon At least one selected from the group consisting of alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, halogen atoms, cyano groups, hydroxyl groups, nitro groups, and carboxy groups It may be further substituted with groups. A plurality of these substituents may be bonded to each other to form a ring.

In the present specification, the substituent further substituted on the substituent in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, It is preferably at least one group selected from the group consisting of an alkyl group having 1 to 25 carbon atoms (straight chain or branched chain alkyl group), a halogen atom, and a cyano group. More preferably, it is at least one group selected from the specific substituents described above.

(Electronics)
An electronic device which is one embodiment of the present invention includes the organic electroluminescence element which is one embodiment of the present invention.
The organic electroluminescent element which is one embodiment of the present invention can be used for various electronic devices. For example, the organic electroluminescence element which is one embodiment of the present invention can be used for a planar light emitter, a backlight, a light source such as an instrument, a display board, a marker lamp, and the like. Examples of the flat light emitter include a flat panel display of a wall-mounted television. Examples of the backlight include backlights such as copying machines, printers, and liquid crystal displays.
Moreover, the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.

[Modification of Embodiment]
In addition, this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are contained in this invention.

In the above embodiment, the mode in which the composition is included in the light emitting layer is described as an example. As another aspect, the organic EL element of the aspect by which the composition is contained in one layer of organic layers other than a light emitting layer is mentioned, for example. For example, an anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport zone included between the light-emitting layer and the cathode, The aspect of the organic EL element containing the composition which concerns on embodiment is illustrated.

For example, the light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked. When the organic EL element has a plurality of light emitting layers, it is sufficient that at least one light emitting layer satisfies the conditions described in the above embodiment. For example, the other light-emitting layer may be a fluorescent light-emitting layer or a phosphorescent light-emitting layer that utilizes light emission by electron transition from a triplet excited state to a direct ground state.
In addition, when the organic EL element has a plurality of light emitting layers, these light emitting layers may be provided adjacent to each other, or a so-called tandem organic material in which a plurality of light emitting units are stacked via an intermediate layer. It may be an EL element.

Further, for example, a barrier layer may be provided adjacent to at least one of the anode side and the cathode side of the light emitting layer. The barrier layer is preferably disposed in contact with the light emitting layer and blocks at least one of holes, electrons, and excitons.
For example, when a barrier layer is disposed in contact with the cathode side of the light-emitting layer, the barrier layer transports electrons, and holes reach a layer on the cathode side of the barrier layer (for example, an electron transport layer). To stop doing. When an organic EL element contains an electron carrying layer, it is preferable to contain the said barrier layer between a light emitting layer and an electron carrying layer.
Further, when a barrier layer is disposed in contact with the anode side of the light emitting layer, the barrier layer transports holes, and the electrons are directed to a layer on the anode side of the barrier layer (for example, a hole transport layer). Stop reaching. When the organic EL element includes a hole transport layer, it is preferable to include the barrier layer between the light emitting layer and the hole transport layer.
Further, a barrier layer may be provided adjacent to the light emitting layer so that excitation energy does not leak from the light emitting layer to the peripheral layer. The excitons generated in the light emitting layer are prevented from moving to a layer (for example, an electron transport layer or a hole transport layer) closer to the electrode than the barrier layer.
The light emitting layer and the barrier layer are preferably joined.

In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

Hereinafter, examples according to the present invention will be described. The present invention is not limited by these examples.

<Compound>
The compound used for manufacture of an organic EL element is shown below.

<Synthesis Example>
(Synthesis Example 1)
Examples of the synthesis of compound PGH-N1 are shown below.

(1) Synthesis of 3-bromo-5-chlorobenzaldehyde Under an argon atmosphere, 692 g of 3,5-dibromochlorobenzene, 1.75 L of dehydrated diether, and 5.25 L of dehydrated toluene were charged into a flask and cooled to −60 ° C. 1.6 L of 1.6 M n-butyllithium hexane solution was added dropwise, and the mixture was stirred at −60 ° C. for 1 hour. After stirring, 595 g of N, N-dimethylformamide was added dropwise, and the reaction was continued at -60 ° C. for 1 hour. After completion of the reaction, 2 L of 1N hydrochloric acid aqueous solution was added. The reaction solution was extracted with toluene, the organic layer was washed with water, dehydrated with magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography to obtain 745 g of 3-bromo-5-chlorobenzaldehyde. DMF is an abbreviation for N, N-dimethylformamide.

(2) Synthesis of N-[(3-bromo-5-chlorophenyl) methylene] benzeneamine Under an argon atmosphere, 745 g of 3-bromo-5-chlorobenzaldehyde, 238 g of aniline, and 5 L of toluene were charged into a flask at 110 ° C. Stirring was continued for 18 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was concentrated to dryness to obtain 702 g of N-[(3-bromo-5-chlorophenyl) methylene] benzenamine.

(3) Synthesis of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine 702 g of N-[(3-bromo-5-chlorophenyl) methylene] benzenamine, benzamidine hydrochloride A flask was charged with 746 g of salt, 10.5 L of dehydrated ethanol, and 286 g of sodium hydroxide, and stirred at 80 ° C. for 20 hours. The mixture was cooled to room temperature, and the precipitated crystals were collected by filtration. The obtained crystals were recrystallized from toluene to obtain 150 g of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine.

(4) Synthesis of 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine 2- (3-bromo-5-chlorophenyl) -4,6 under argon atmosphere Add 8.45 g of diphenyl-1,3,5-triazine, 2.68 g of phenylboronic acid, 0.693 g of tetrakistriphenylphosphine palladium (0), 30 mL of 2M aqueous sodium carbonate solution, and 60 mL of toluene to the flask and add 100 ° C. And stirred for 24 hours. After cooling to room temperature, the aqueous layer was removed, and the organic layer was washed with saturated brine and then dried over magnesium sulfate. The organic layer was concentrated, and the residue was purified by silica gel column chromatography to obtain 5.50 g of 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine.

(5) Synthesis of Compound PGH-N1 Under an argon atmosphere, 1.67 g of 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine, 9′-phenyl-9H, 1.6 'g of 9'H-2,3-bicarbazole, 0.073 g of trisdibenzylideneacetone dipalladium (0), 0.092 g of tri-t-butylphosphonium tetrafluoroborate, 1.15 g of sodium t-butoxy, and 40 mL of xylene Was stirred in a flask at 140 ° C. for 6 hours. After cooling to room temperature, the reaction solution was concentrated. The residue was purified by silica gel column chromatography to obtain 1.92 g of a yellow solid. As a result of mass spectrum analysis, this yellow solid was the target product (Compound PGH-N1), and the molecular weight was 791.30, and m / e = 791.

(Synthesis Example 2)
Examples of the synthesis of compound PGH-N2 are shown below.

Under an argon atmosphere, 4.63 g of 2- (3-bromophenyl) -4- (3-biphenyl) -6-phenyl-1,3,5-triazine, 9′-phenyl-9H, 9′H-2,3 A flask was charged with 4.50 g of bicarbazole, 0.183 g of trisdibenzylideneacetone dipalladium (0), 0.116 g of tri-t-butylphosphonium tetrafluoroborate, 1.35 g of t-butoxy sodium, and 40 mL of xylene, and 140 ° C. And stirred for 6 hours. After cooling to room temperature, the reaction solution was concentrated. The residue was purified by recrystallization to obtain 4.23 g of a yellow solid. As a result of mass spectrum analysis, this yellow solid was the target product (compound PGH-N2), and the molecular weight was 791.30, and m / e = 791.

(Synthesis Example 3)
Examples of the synthesis of compound PGH-N3 are shown below.

In the synthesis of compound PGH-N2, instead of 2- (3-bromophenyl) -4- (3-biphenyl) -6-phenyl-1,3,5-triazine, 2- (3′-bromobiphenyl-3- Yl) -4,6-diphenyl-1,3,5-triazine was used in the same manner as in Synthesis Example 2 to obtain compound PGH-N3. As a result of mass spectrum analysis, the compound obtained by this synthesis was the target product (compound PGH-N3), which had a molecular weight of 791.30 and m / e = 791.

<Production of organic EL element>
An organic EL element was produced as follows.

Example 1
1.1 g of compound PGH-P1 was measured, 1.1 g of compound PGH-N1 was measured, and these two compounds were mixed in a mortar. After mixing, 2 g of the mixture was filled in a quartz crucible for a vacuum evaporation apparatus. A part of the mixture of compound PGH-P1 and compound PGH-N1 in the crucible was collected, the collected material was dissolved in tetrahydrofuran, and the compound PGH was calculated from the peak area values of each component detected by HPLC (High Performance Liquid Chromatography). When the ratio of -P1 to compound PGH-N1 was measured, the mass ratio (initial ratio) was compound PGH-P1: compound PGH-N1 = 5: 5.
A crucible filled with the mixture of compound PGH-P1 and compound PGH-N1, a crucible filled with compound HAT, a crucible filled with compound HT-1, a crucible filled with compound HT-2, and filled with compound PGD-1 The crucible, the crucible filled with compound ET-1, and the crucible filled with 8-quinolinolatolithium (Liq) were set in a vacuum deposition apparatus.

A glass substrate (manufactured by Geomat Co.) with an ITO transparent electrode (anode) having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The film thickness of ITO was 130 nm. Mount the glass substrate with the transparent electrode line after cleaning on the substrate holder of the vacuum evaporation system and protect one side with a mask. Compound HAT was vapor-deposited to form a HAT film having a thickness of 10 nm to form a hole injection layer.
Next, a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
Next, a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
Next, a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm. The concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
Subsequent to the formation of the light-emitting layer, the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. .
Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm.
Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm.
The organic EL device produced in this way was used as an organic EL device in the initial stage of vapor deposition.

After manufacturing the organic EL element, the ITO substrate is retracted out of the chamber, and the mixture of the compound PGH-P1 and the compound PGH-N1 is evaporated to a mass of 0.4 g (the remaining amount is 20% by mass). ) Continued until. Thereafter, the ITO substrate is returned to the chamber, and the already prepared organic EL element part is protected with a mask, and then the compound HAT is vapor deposited so as to cover the transparent electrode on the surface on which the transparent electrode line is formed. A HAT film having a thickness of 10 nm was formed to form a hole injection layer.
Next, a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
Next, a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
Next, a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm. The concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
Subsequent to the formation of the light-emitting layer, the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. .
Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm.
Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm.
The organic EL device produced in this way was used as the organic EL device at the end of vapor deposition.
Finally, the residue in the crucible is taken out from the vapor deposition apparatus, the residue in the crucible is dissolved in tetrahydrofuran, and the ratio (residue ratio) of compound PGH-P1 and compound PGH-N1 from the peak area values of each component detected by HPLC Asked.

Table 1 shows the ratio (initial ratio) of the compound PGH-P1 and the compound PGH-N1 in the crucible in the initial stage (before deposition), and the ratio of the compound PGH-P1 and the compound PGH-N1 in the crucible after deposition ( Residue ratio).

(Example 2)
Example 2 was carried out in the same manner as Example 1 except that compound PGH-N2 was used instead of compound PGH-N1 in the light emitting layer of Example 1.
Table 1 shows the ratio (initial ratio) of compound PGH-P1 and compound PGH-N2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-P1 and compound PGH-N2 in the crucible after vapor deposition ( Residue ratio).

(Example 3)
Example 3 was carried out in the same manner as Example 1 except that compound PGH-N3 was used instead of compound PGH-N1 in the light emitting layer of Example 1.
Table 1 shows the ratio (initial ratio) of compound PGH-P1 and compound PGH-N3 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-P1 and compound PGH-N3 in the crucible after vapor deposition ( Residue ratio).

(Comparative Example 1)
Comparative Example 1 uses Compound PGH-C1 instead of Compound PGH-P1 in the light emitting layer of Example 1, and uses Compound PGH-C2 instead of Compound PGH-N1 in the light emitting layer of Example 1. This was carried out in the same manner as in Example 1 except that.
Table 1 shows the ratio (initial ratio) of compound PGH-C1 and compound PGH-C2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-C1 and compound PGH-C2 in the crucible after vapor deposition ( Residue ratio).

In the organic EL device in the initial stage of vapor deposition according to Example 1, the mass ratio (film ratio) of the compound PGH-P1 and the compound PGH-N1 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-P1: the compound PGH- N1 = 5: 5.

In the organic EL element in the initial stage of vapor deposition according to Example 2, the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N2 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-P1: the compound PGH- N2 = 5: 5.

In the organic EL element in the initial stage of vapor deposition according to Example 3, the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N3 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-P1: the compound PGH- N3 = 5: 5.

In the organic EL device in the initial stage of vapor deposition according to Comparative Example 1, the mass ratio (film ratio) of the compound PGH-C1 and the compound PGH-C2 in the light emitting layer was analyzed by HPLC. C2 = 8: 2.

Regarding the organic EL elements of Examples 1 to 3 (initial stage of vapor deposition), the mass ratio (film ratio) between the first compound and the second compound in the light emitting layer was the first (before vapor deposition) in the first crucible in the crucible. The ratio was the same as the mass ratio (initial ratio) between the compound and the second compound.
On the other hand, regarding the organic EL element of Comparative Example 1 (initial stage of vapor deposition), the mass ratio (film ratio) of the compound PGH-C1 and the compound PGH-C2 in the light emitting layer was the compound PGH in the crucible at the initial stage (before vapor deposition). The mass ratio (initial ratio) of -C1 and compound PGH-C2 was significantly different. In Comparative Example 1, compound PGH-C1 and compound PGH-C2 were mixed in a mass ratio of 5: 5 in the crucible, but the mass ratio in the film was 8: 2, and the ratio in the light emitting layer It was found that the film was not formed at the same rate as the material charge ratio.

<Evaluation of organic EL element>
The following evaluations were performed on the organic EL elements at the initial stage of vapor deposition and the organic EL elements at the end of the vapor deposition produced in Examples 1 to 3 and Comparative Example 1. The evaluation results are shown in Table 2.

・ Drive voltage V
The voltage (unit: V) when energized between the ITO transparent electrode and the metal Al cathode was measured so that the current density was 10 mA / cm ² .

・ External quantum efficiency EQE
A spectral radiance spectrum when a voltage was applied to the device so that the current density was 10 mA / cm ² was measured with a spectral radiance meter CS-1000 (manufactured by Konica Minolta). The external quantum efficiency EQE (unit:%) was calculated from the obtained spectral radiance spectrum, assuming that Lambtian radiation was performed.

・ Lifetime LT97
A DC continuous energization test was performed with the initial current density set to 10 mA / cm ² , the time when the luminance decreased to 97% with respect to the luminance at the start of the test was measured, and the measured time was determined as the lifetime LT97 ( Unit: hours (hrs)).

According to Examples 1 to 3, it was found that there was less variation in device performance compared to Comparative Example 1 with respect to the organic EL device at the initial stage of vapor deposition and the organic EL device at the end of the vapor deposition. While maintaining the performance of the organic electroluminescence device by using the composition containing the first compound represented by the general formula (1) and the second compound represented by the general formula (2), It has been found that the ratio of materials can be stably deposited from one deposition source.

DESCRIPTION OF SYMBOLS 1 ... Organic EL element, 3 ... Anode, 4 ... Cathode, 5 ... Light emitting layer, 7 ... Hole transport layer, 8 ... Electron transport layer.

Claims

A composition in which two or more compounds are mixed,
A composition containing at least a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2).

(In the general formula (1),
R 1 to R 4 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
A 1 and A 2 are each independently
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 6 to 30 ring atoms.
However, a total of six ring structures represented by the following general formula (1a) are included in R 1 to R 4 , A 1 and A 2 . )

(In the general formula (1a), X 1 , X 2 and X 3 each independently represent C R X or N. At least one of the six ring structures represented by the general formula (1a) In the ring structure, at least one of X 1 , X 2 and X 3 represents N. When the ring structures represented by the general formula (1a) are bonded to form a condensed ring, There are cases where it does not.
R X , R X1 , R X2 and R X3 are each independently
Single bond,
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
When a plurality of R x are present, the plurality of R X are the same as or different from each other.
At least one of R X1 , R X2 , R X3 and one or more R X is a single bond. )

(In the general formula (2), R 21 to R 24 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 30 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3, or 4;
f is 0, 1, 2, or 3.
g is 0, 1, 2, or 3.
h is 0, 1, 2, 3, or 4.
When e is 2 or more, the plurality of R 21 are the same as or different from each other.
When f is 2 or more, the plurality of R 22 are the same as or different from each other.
When g is 2 or more, the plurality of R 23 are the same as or different from each other.
When h is 2 or more, the plurality of R 24 are the same as or different from each other.
At least one of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b).

(In the general formula (2a), Ar represents a substituted or unsubstituted triphenylenylene group.)

(In the general formula (2b), X 4 , X 5 , X 6 , X 7 and X 8 each independently represent CR Y or N. R Y represents
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Y are the same as or different from each other. )
The composition of claim 1, wherein
The composition wherein the first compound is a compound represented by the following general formula (3).

(In the general formula (3),
R 1 to R 6 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
i is 0, 1, 2, 3, or 4.
j is 0, 1, 2, 3, 4, or 5.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
When i is 2 or more, the plurality of R 5 are the same as or different from each other.
When j is 2 or more, the plurality of R 6 are the same as or different from each other.
B 1 represents a substituent represented by the following general formula (4) or the following general formula (5). )

(In the general formula (4) and the general formula (5),
X 1 to X 3 each represent CR Z or a nitrogen atom.
R Z is
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other.
R 7 to R 9 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A cyano group is shown.
k is 0, 1, 2, 3, 4, or 5.
l is 0, 1, 2, 3, 4, or 5;
m is 0, 1, 2, 3, or 4.
When k is 2 or more, the plurality of R 7 are the same as or different from each other.
When l is 2 or more, the plurality of R 8 are the same as or different from each other.
When m is 2 or more, the plurality of R 9 are the same as or different from each other. )
The composition of claim 1, wherein
The composition wherein the first compound is a compound represented by the following general formula (6).

(In the general formula (6),
R 1 to R 6 and R 10 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3, or 4;
b is 0, 1, 2, or 3;
c is 0, 1, 2, or 3;
d is 0, 1, 2, 3 or 4.
i is 0, 1, 2, or 3.
j is 0, 1, 2, 3, 4, or 5.
n is 0, 1, 2, 3, 4, or 5.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
When i is 2 or more, the plurality of R 5 are the same as or different from each other.
When j is 2 or more, the plurality of R 6 are the same as or different from each other.
When n is 2 or more, the plurality of R 10 are the same as or different from each other.
B 2 represents a substituent represented by the following general formula (7). )

(In the general formula (7),
X 1 to X 3 each represent CR Z or a nitrogen atom.
R Z is
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other.
R 11 and R 12 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
o is 0, 1, 2, 3, 4, or 5.
p is 0, 1, 2, 3, 4, or 5.
When o is 2 or more, the plurality of R 11 are the same as or different from each other.
When p is 2 or more, the plurality of R 12 are the same as or different from each other. )
In the composition according to any one of claims 1 to 3,
A composition in which X 1 , X 2 , and X 3 in at least any one of the six ring structures represented by the general formula (1a) are nitrogen atoms.
In the composition according to any one of claims 1 to 4,
A composition wherein a, b, c, d, k, l, m, n, o and p are 0.
In the composition according to any one of claims 1 to 5,
The composition wherein the second compound is a compound represented by the following general formula (8).

(In the general formula (8), R 21 to R 24 are each independently
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3, or 4;
f is 0, 1, 2, or 3.
g is 0, 1, 2, or 3.
h is 0, 1, 2, 3, or 4.
When e is 2 or more, the plurality of R 21 are the same as or different from each other.
When f is 2 or more, the plurality of R 22 are the same as or different from each other.
When g is 2 or more, the plurality of R 23 are the same as or different from each other.
When h is 2 or more, the plurality of R 24 are the same as or different from each other.
At least one of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by (2b).

(In the general formula (2a), Ar represents a substituted or unsubstituted triphenylenylene group.)

(In the general formula (2b), X 4 , X 5 , X 6 , X 7 and X 8 each independently represent CR Y or N. R Y represents
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Y are the same as or different from each other. )
In the composition according to any one of claims 1 to 6,
X 4 , X 5 , X 6 , X 7 and X 8 are CR Y ,
R Y is
Hydrogen atom,
A halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group;
The plurality of R Y are the same as or different from each other.
In the composition according to any one of claims 1 to 7,
A composition wherein Ar is an unsubstituted divalent triphenylenylene group.
Material for organic electroluminescent elements containing the composition as described in any one of Claims 1-8.
A composition film comprising the composition according to any one of claims 1 to 8.
An anode, a cathode, and an organic layer included between the anode and the cathode,
The organic layer includes the composition according to any one of claims 1 to 8.
Organic electroluminescence device.
The organic electroluminescence device according to claim 11,
The organic layer is composed of a plurality of layers,
The said composition is an organic electroluminescent element contained in one layer of the said some layer.
In the organic electroluminescent element according to claim 11 or 12,
The organic layer includes a light emitting layer,
The said light emitting layer is an organic electroluminescent element containing the said composition.
The organic electroluminescence device according to claim 13,
An organic electroluminescence device, wherein the light emitting layer further contains a light emitting material.
The organic electroluminescence device according to claim 14,
The light emitting layer contains a phosphorescent light emitting material as the light emitting material,
The organic light-emitting device, wherein the phosphorescent material is an orthometalated complex of any metal atom selected from the group consisting of iridium, osmium, and platinum.
In the organic electroluminescent element according to any one of claims 13 to 15,
An organic electroluminescence device further comprising a hole transport layer between the anode and the light emitting layer.
The organic electroluminescence device according to any one of claims 13 to 16,
An organic electroluminescence device further comprising an electron transport layer between the cathode and the light emitting layer.
An anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport band included between the light-emitting layer and the cathode,
The electron transport zone comprises the composition according to any one of claims 1 to 8.
Organic electroluminescence device.
An electronic device equipped with the organic electroluminescence element according to any one of claims 11 to 18.