JP2021147325A - Aromatic compound - Google Patents

Abstract

To provide an aromatic compound which has excellent heat resistance and not too high charge transportability in a luminous layer.SOLUTION: The invention provides an aromatic compound represented by the general formula (1) in the figure, where R1, R2 and R3 are each as defined in the specification.SELECTED DRAWING: Figure 1

Description

The present invention relates to aromatic compounds having high thermal durability.
The present invention also includes an organic electroluminescent device having the compound (hereinafter, may be referred to as "OLED" or "element"), a composition containing the compound and the solvent, and the organic electroluminescent device. Regarding lighting equipment and display equipment.
The present invention also relates to a thin film forming method and a method for manufacturing an organic electroluminescent device.

In recent years, as a thin film type electroluminescent device, an organic electroluminescent device using an organic thin film has been developed instead of one using an inorganic material. An organic electroluminescent device (OLED) usually has a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and the like between an anode and a cathode. Materials suitable for each of these layers are being developed, and the emission colors are red, green, and blue, respectively. In addition, research on a coating type OLED that has higher material utilization efficiency and can reduce the manufacturing cost as compared with the conventional thin-film deposition type is underway.

In the coating type OLED, it is required to extend the life of the element and drive it with lower power consumption. Various factors can be considered as factors that affect the life and power consumption improvement of the device. For example, it is considered that the thermal durability and crystallinity of the materials constituting the device have a great influence on the life. ..

Further, in order to manufacture an organic electroluminescent device by a wet film forming method, all the materials used must be soluble in an organic solvent and can be used as ink. If the material used is inferior in solubility, operations such as heating for a long time are required, so that the material may deteriorate before use. Further, if the uniform state cannot be maintained for a long time in the solution state, the material is precipitated from the solution, and the film formation by an inkjet device or the like becomes impossible. The material used in the wet film forming method is required to have solubility in two meanings: that it dissolves quickly in an organic solvent, and that it does not precipitate after being dissolved and maintains a uniform state.

In an organic electroluminescent element using an organic thin film made of a plurality of low molecular weight materials formed by a wet film formation method, Non-Patent Document 1 describes an element using phosphorescence emission in order to increase the luminous efficiency of the element. ing. The following biphenyl derivatives are used as the charge transport material for the organic electroluminescent device described in Non-Patent Document 1.

Further, Patent Documents 1 and 2 report materials for OLEDs using a nitrogen-containing polycondensed ring compound as a host compound of a phosphorescent compound.

International Publication No. 2015/014434 Japanese Patent Application Laid-Open No. 2013-510803

Japanese Journal of Applied Physics Vol.44, No.1B, 2005, pp.626-629

However, the compound described in Non-Patent Document 1, the compound described in Patent Document 1, and the compound described in Patent Document 2 have high charge transportability in the light emitting layer, and the life of the organic electroluminescent element having the compound is long. May decrease.

Further, the compound described in Non-Patent Document 1, the compound described in Patent Document 1, and the compound described in Patent Document 2 do not have sufficient heat resistance.

The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide an aromatic compound having excellent heat resistance by appropriately relaxing the charge transport property in an organic layer such as a light emitting layer. do.

Another object of the present invention is to provide an organic electroluminescent element having the compound, a composition containing the compound and the solvent, and a lighting device and a display device having the organic electroluminescent element. Another object of the present invention is to provide a thin film forming method and a method for manufacturing an organic electroluminescent device using the composition.

As a result of diligent studies by the present inventors, by using an aromatic compound having a specific structure containing a dibenzofuran structure, the aromatic compound appropriately relaxes the charge transport property in an organic layer such as a light emitting layer, and Tg. We have found that (glass transition temperature) is high and has excellent heat resistance, and have reached the present invention.
That is, the gist of the present invention lies in the following <1> to <10>.

<1> An aromatic compound represented by the following general formula (1).

In the formula (1), R ¹ and R ² are independent of each other and are represented by the following general formula (2) or the following general formula (3), and R ³ is an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group. , Aryloxy group, alkoxycarbonyl group, acyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group, silyl group, syroxy group, cyano group, or aralkyl group, and a is an integer of 0 to 6. However, ^{at least one of R 1} and R ² is represented by the following general formula (2).

In the formula (2), the asterix (*) represents a bond with the formula (1), and Ar ¹ is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. n is an integer of 1 or more.

In the formula (3), the asterix (*) represents a bond with the formula (1), and Ar ² is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ is a monovalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent, and m is an integer of 1 or more.
<2> An organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode.
An organic electroluminescent element, wherein the organic layer has a layer containing a material for an organic electroluminescent element, and the material for the organic electroluminescent element is an aromatic compound according to <1>.
<3> The organic electroluminescent device according to <2>, wherein the layer containing the material for the organic electroluminescent device is a light emitting layer.
<4> A display device having the organic electroluminescent device according to <2> or <3>.
<5> A lighting device having the organic electroluminescent device according to <2> or <3>.
<6> A composition containing the aromatic compound and solvent according to <1>.
<7> The composition according to <6>, which further contains a phosphorescent material and a host material.
<8> A thin film forming method comprising a step of forming a film of the composition according to <6> or <7> by a wet film forming method.
<9> A method for manufacturing an organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode.
A method for producing an organic electroluminescent device, which comprises a step of forming the organic layer by a wet film forming method using the composition according to <6> or <7>.
<10> The method for manufacturing an organic electroluminescent device according to <9>, wherein the organic layer is a light emitting layer.

The aromatic compound of the present invention appropriately relaxes the charge transport property in an organic layer such as a light emitting layer, and has excellent heat resistance. Further, since the aromatic compound of the present invention has excellent solubility in various solvents and has amorphousness, it is possible to form a thin film by a wet film forming method.

Therefore, using the aromatic compound of the present invention, it is possible to easily provide an organic electroluminescent device which is excellent in drive stability and can be driven with a low drive voltage.

The organic electroluminescent element of the present invention, which includes a light emitting layer formed by using the aromatic compound of the present invention, has excellent electrochemical stability, a low driving voltage, and high efficiency. Therefore, it is a flat panel display. (For example, OA computer displays and wall-mounted TVs), in-vehicle display elements, light sources that take advantage of the characteristics of mobile phone displays and surface emitters (for example, light sources for copying machines, backlight sources for liquid crystal displays and instruments), displays It can be applied to boards and indicator lights, and its technical value is great.

FIG. 1 is a cross-sectional view schematically showing an example of the structure of the organic electroluminescent device of the present invention.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

In the present invention, "may have a substituent" means that it may have one or more substituents.

<Aromatic compound of the present invention>
The aromatic compound of the present invention is an aromatic compound having a structure containing a dibenzofuran structure represented by the following general formula (1).

In the formula (1), R ¹ and R ² are independent of each other and are represented by the following general formula (2) or the following general formula (3), and R ³ is an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group. , Aryloxy group, alkoxycarbonyl group, acyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group, silyl group, syroxy group, cyano group, or aralkyl group, and a is an integer of 0 to 6. However, ^{at least one of R 1} and R ² is represented by the following general formula (2).

In the formula (2), the asterix (*) represents the bond with the dibenzofuran structure of the formula (1), and Ar ¹ is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. And n is an integer of 1 or more.

In the formula (3), the asterix (*) represents the bond with the dibenzofuran structure of the formula (1), and Ar ² is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ is a monovalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent, and m is an integer of 1 or more.

When a is 2 or more, a plurality of R ^3s may be the same or different. R ³ is preferably an alkyl group, an alkoxy group, or an aralkyl group. Specific examples and preferable ranges of R ³ are the same as those of the corresponding substituents in the substituent group Z described later.
Further, the aromatic compound of the present invention is preferably an aromatic compound represented by the following general formula (1a) when a is 0, that is, from the viewpoint of durability and heat resistance.

In the formula (1a), ^{R 1} and ^{R 2} definitions are as defined for ^{R 1} and ^{R 2} in the formula (1).

Since the compound represented by the general formula (1) of the present invention has aromatic ring groups at the 1- and 2-positions of the dibenzofuran skeleton, the intermolecular interaction is reduced due to steric hindrance, and the crystallinity is lowered. Therefore, it is considered that the charge transport property in the light emitting layer can be suppressed.

Furthermore, since the compound represented by the general formula (1) of the present invention has two or more dibenzofuran skeletons, it has excellent heat resistance.

<Ar ¹ >
In the formula (2), Ar ¹ represents a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Examples of aromatic hydrocarbon groups having 20 or less carbon atoms include a benzene ring, a naphthalene ring, a phenanthrene ring, a chrysene ring, a pyrene ring, a benzoanthracene ring, and a perylene ring. From the viewpoint of the solubility of the compound, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.

From the viewpoint of the solubility and heat resistance of the compound, n is more preferably 2 or more, preferably 7 or less, more preferably 5 or less, further preferably 4 or less, and particularly preferably 3 or less.

when n is 2 or more, a plurality of Ar ¹ may be the same or different.
If the Ar ¹ there are a plurality, it is preferable that all the Ar ¹ is a benzene ring.
Note that n is the number of repetitions of ^{Ar 1.}

<Ar ² >
In the formula (3), Ar ² is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Examples of aromatic hydrocarbon groups having 20 or less carbon atoms include a benzene ring, a naphthalene ring, a phenanthrene ring, a chrysene ring, a pyrene ring, a benzoanthracene ring, and a perylene ring. From the viewpoint of the solubility of the compound, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.

From the viewpoint of the solubility and heat resistance of the compound, m is more preferably 2 or more, further preferably 3 or more, preferably 7 or less, more preferably 5 or less, still more preferably 4 or less.

when m is 2 or more, a plurality of Ar ² may be the same or different.
If Ar ² there are a plurality, more preferably all of Ar ² is benzene ring.
Note that m is the number of repetitions of ^{Ar 2.}

<Ar ³ >
In the formula (3), Ar ³ is a monovalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Examples of aromatic hydrocarbon groups having 20 or less carbon atoms include a benzene ring, a naphthalene ring, a phenanthrene ring, a chrysene ring, a pyrene ring, a benzoanthracene ring, and a perylene ring. From the viewpoint of compound solubility and heat resistance, a benzene ring, a naphthalene ring, and a phenanthrene ring are preferable, and a benzene ring is more preferable.

<(Ar ¹ ) _n , (Ar ² ) _m >
At least one of (Ar ¹ ) _n and (Ar ² ) _m has a partial structure represented by the following formula (11) and a partial structure represented by the following formula (12) from the viewpoint of compound solubility and heat resistance. , And at least one partial structure selected from the partial structures represented by the following formula (13).

In each of the above formulas (11) to (13), * represents a bond with an adjacent structure or a hydrogen atom, and at least one of two * exists represents a bond position with an adjacent structure.

More preferably ^{, at least one of (Ar 1} ) _n and (Ar ² ) _m has at least a partial structure represented by the formula (11) or a partial structure represented by the formula (12).
More preferably, (Ar ¹ ) _n and (Ar ² ) _m have at least a partial structure represented by the formula (11) or a partial structure represented by the formula (12), respectively.
Particularly preferably, (Ar ¹ ) _n and (Ar ² ) _m have a partial structure represented by the formula (11) and a partial structure represented by the formula (12), respectively.

The formula (12) is preferably the following formula (12-2).

Further, it is represented by the following formulas (14) to (18), which is a structure including a plurality of structures selected from the partial structure represented by the formula (11) and the partial structure represented by the formula (12). Substructures are even more preferred.

The structure including a plurality of structures selected from the partial structure represented by the formula (11) and the partial structure represented by the formula (12) is, for example, the formula (14) is expressed by the following formula (14a). It is a partial structure having one partial structure represented by (11) and two partial structures represented by the formula (12).

Further, more preferably ^{, at least one of (Ar 1} ) _n and (Ar ² ) _m has at least a partial structure represented by the formula (15) or a partial structure represented by the formula (17).

The formula (15) is preferably the following formula (15-2).

The formula (17) is preferably the following formula (17-2).

The formula (18) is preferably the following formula (18-2).

Further, as the structure including the partial structure represented by the formula (13), it is more preferable to have the partial structure represented by the following formula (19) or the partial structure represented by the following formula (20).

In each of the above formulas (14) to (20), * represents a bond with an adjacent structure or a hydrogen atom, and at least one of two * exists represents a bond position with an adjacent structure.

< ^{Substituents that Ar 1 to} Ar ³ may have>
The ^{substituents that Ar 1 to} Ar ³ may have can be selected from, for example, the substituent group Z described later.

[Substituent group Z]
The substituent group Z includes an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group and a cyano group. , Aralkyl group or aromatic hydrocarbon group.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group and a cyclohexyl group. , Dodecyl group and the like, which usually have 1 or more carbon atoms, preferably 4 or more carbon atoms, usually 24 or less, preferably 12 or less carbon atoms, and examples thereof include linear, branched, or cyclic alkyl groups.

Examples of the alkenyl group include an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group.

Examples of the alkynyl group include an alkynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an ethynyl group.

Examples of the alkoxy group include an alkoxy group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less, such as a methoxy group and an ethoxy group.

Examples of the aryloxy group include an aryloxy group such as a phenoxy group, a naphthoxy group, and a pyridyloxy group, which usually has 4 or more carbon atoms, preferably 5 or more carbon atoms, and usually 36 or less, preferably 24 aryloxy groups or heteroaryloxy groups. The group is mentioned.

Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the acyl group include an acyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an acetyl group and a benzoyl group.

Examples of the halogen atom include a halogen atom such as a fluorine atom and a chlorine atom.

Examples of the haloalkyl group include a haloalkyl group having a carbon number of usually 1 or more, usually 12 or less, preferably 6 or less, such as a trifluoromethyl group.

Examples of the alkylthio group include an alkylthio group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less, such as a methylthio group and an ethylthio group.

Examples of the arylthio group include an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, and a pyridylthio group.

Examples of the silyl group include a silyl group having a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less, such as a trimethylsilyl group and a triphenylsilyl group.

Examples of the syroxy group include syroxy groups having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsiloxy group and a triphenylsyloxy group.

Examples of the aralkyl group include an aralkyl group having a carbon number of usually 7 or more, preferably 10 or more, and usually 30 or less, preferably 18 or less, such as a benzyl group and a 2-phenylethyl group.

Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group.

Examples of alkyl groups having 10 or less carbon atoms include methyl group, ethyl group, branched, linear or cyclic propyl group, branched, linear or cyclic butyl group, branched, linear or cyclic pentyl group, branched. , Linear or cyclic hexyl group, branched, linear or cyclic octyl group, branched, linear or cyclic nonyl group, branched, linear or cyclic decyl group. From the viewpoint of the stability of the compound, a methyl group, an ethyl group, a branched, linear or cyclic propyl group, a branched, linear or cyclic butyl group is preferable, and a branched propyl group is particularly preferable.

Examples of aromatic hydrocarbon groups having 20 or less carbon atoms are monovalent substituents of aromatic rings, such as benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, chrysene ring, pyrene ring, benzoanthracene ring, and perylene ring. And so on. From the viewpoint of compound solubility, a benzene ring and a naphthalene ring are preferable.

Examples of aralkyl groups having 30 or less carbon atoms include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, and a 3-phenylpentyl-3-yl group. , 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, 8-phenyl- 1-Octyl group or the like.

Among the above substituent groups Z, an alkyl group, an alkoxy group, an aromatic hydrocarbon group and an aralkyl group are preferable, and an alkyl group having 10 or less carbon atoms and an aromatic hydrocarbon group having 20 or less carbon atoms are more preferable. It is an aralkyl group having 30 or less carbon atoms, and a benzene ring is more preferable from the viewpoint of heat resistance and durability. Most preferably, Ar ^{1 to} Ar ³ do not have a substituent.

Further, each substituent of the above-mentioned Substituent Group Z may further have a Substituent. As the further substituents thereof, the same ones as those of the above-mentioned substituents (substituent group Z) can be used.

<Specific example>
Specific examples of the aromatic compound represented by the formula (1) will be shown below, but the present invention is not limited thereto.

<Use of aromatic compounds>
The aromatic compound of the present invention can be suitably used as a material used for an organic electroluminescent element, that is, a charge transport material for an organic electroluminescent element, and can also be suitably used as a charge transport material for other light emitting elements and the like. be.

In particular, the aromatic compound of the present invention has a steric hindrance due to having a dibenzofuran ring and an aromatic hydrocarbon group as a basic skeleton and having an aromatic ring group at the 1st and 2nd positions of the dibenzofuran ring. By having an aromatic ring group at the 1-position, steric hindrance with the hydrogen atom at the 8-position causes a greater twist with the dibenzofuran ring than when having an aromatic ring group at another bond position, resulting in higher non-conjugation. It seems that there is a tendency. Further, by having an aromatic ring group at the 1st and 2nd positions as adjacent positions, there is a case where the aromatic ring group is at the conjugated 3rd position, a case where the aromatic ring group is at the 2nd and 3rd positions, and a case where the aromatic ring group is at the 3rd and 3rd positions. The conjugated length is less likely to spread than when it has an aromatic ring group at the position.

Therefore, the aromatic compound of the present invention has a large energy gap (difference between HOMO and LUMO) and a high excited triplet level (T1). Therefore, in the light emitting layer of the organic electroluminescent element, a host material, particularly a phosphorescent material, is used. Useful as a host material.

In particular, the aromatic compound of the present invention can be used for producing an organic electroluminescent device by a vacuum deposition method, and can also form a thin film by a wet film forming method. Therefore, the organic compound applied to the wet film forming method. It is also suitable as a material for electroluminescent devices.

Therefore, if an organic electroluminescent element can be produced by a vacuum deposition method using a material for an organic electroluminescent element made of the aromatic compound of the present invention, a composition for an organic electroluminescent element containing the aromatic compound of the present invention can be used. It is also possible to manufacture an organic electroluminescent element by a wet film forming method.

The obtained organic electroluminescent element has excellent drive stability and can be driven with a low drive voltage.

<Material for organic electroluminescent device>
The material for an organic electroluminescent element of the present invention is made of the aromatic compound of the present invention, and is preferably dissolved in toluene in an amount of 2% by mass or more, more preferably 5% by mass or more.

As will be described later, aromatic hydrocarbons are preferable as the solvent contained in the composition for the organic electroluminescent device. Toluene is mentioned as a typical example of aromatic hydrocarbons, and the solubility in toluene is used as an index indicating the solubility of a material for an organic electroluminescent device.

When the solubility of the material for an organic electroluminescent device of the present invention in toluene is 2% by mass or more, it is preferable that a layer constituting the organic electroluminescent device can be easily formed by a wet film forming method. The upper limit of this solubility is not particularly limited, but is usually about 50% by mass.

<Composition for organic electroluminescent device>
The composition for an organic electroluminescent element of the present invention usually contains the aromatic compound and the solvent of the present invention, and more preferably contains a light emitting material and a host material.

[1] Solvent The solvent contained in the composition for an organic electric field light emitting element of the present invention is not particularly limited as long as it is a solvent in which the aromatic compound of the present invention, which is a solute, dissolves well.

Since the aromatic compound of the present invention has high solubility, various solvents can be applied. For example, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene and tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole. , Fenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic esters such as ethyl, propyl benzoate, n-butyl benzoate; ketones having an alicyclic such as cyclohexanone and cyclooctanone; aliphatic ketones such as methylethyl ketone and dibutylketone; alicyclic such as cyclohexanol and cyclooctanol. Alcohols: Aromatic alcohols such as butanol and hexanol; Aromatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate (PGMEA); ethyl acetate, n-butyl acetate, ethyl lactate, etc. Aromatic esters such as n-butyl lactic acid can be used. Of these, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, and tetralin are preferable because they have low water solubility and do not easily deteriorate.

Since many materials such as cathodes that are significantly deteriorated by moisture are used in organic electroluminescent devices, the presence of moisture in the composition causes moisture to remain in the film after drying, which deteriorates the characteristics of the device. There is a possibility and it is not preferable.

Examples of the method for reducing the amount of water in the composition include using a nitrogen gas seal, using a desiccant, pre-dehydrating the solvent, and using a solvent having low water solubility. Among them, when a solvent having a low water solubility is used, it is preferable because the phenomenon that the solution film absorbs the moisture in the atmosphere and whitens during the wet film forming step can be prevented.

From such a viewpoint, the composition for an organic electroluminescent element of the present invention contains, for example, a solvent having a solubility of water at 25 ° C. of 1% by mass or less, preferably 0.1% by mass or less in the composition. It is preferably contained in an amount of% by mass or more.

Further, in order to reduce a decrease in film formation stability due to solvent evaporation from the composition during wet film formation, the composition for an organic electroluminescent element has a boiling point of 100 ° C. or higher, preferably a boiling point of 150. It is effective to use a solvent having a boiling point of 200 ° C. or higher, more preferably 200 ° C. or higher.

Further, in order to obtain a more uniform film, it is necessary for the solvent to evaporate from the liquid film immediately after the film formation at an appropriate rate, and for this purpose, the boiling point is usually 80 ° C. or higher, preferably 100 ° C. or higher. It is more effective to use a solvent having a boiling point of 120 ° C. or higher, usually a boiling point of less than 270 ° C., preferably a boiling point of less than 250 ° C., and more preferably a boiling point of less than 230 ° C.

A solvent that satisfies the above-mentioned conditions, that is, the conditions of solute solubility, evaporation rate, and water solubility, may be used alone, or two or more kinds of solvents may be mixed and used.

[2] Light-emitting material The composition for an organic electroluminescent device of the present invention preferably further contains a light-emitting material. The light emitting material mainly refers to a component that emits light in the composition for an organic electroluminescent element of the present invention, and corresponds to a dopant component in an organic electroluminescent device. That is, of the amount of light (unit: cd / m ² ) emitted from the composition for an organic electroluminescent device, it is usually 10 to 100%, preferably 20 to 100%, more preferably 50 to 100%, and most preferably 80 to 80. If 100% is identified as luminescent from a component material, it is defined as a luminescent material.

As the light emitting material, a known material can be applied, and a fluorescent light emitting material or a phosphorescent light emitting material can be used alone or in combination of two or more, but from the viewpoint of internal quantum efficiency, a phosphorescent light emitting material is preferable.

When used in the composition for an organic electroluminescent device of the present invention, the maximum emission peak wavelength of this light emitting material is preferably in the range of 390 to 490 nm.

It is also important to reduce the symmetry and rigidity of the luminescent material molecule or to introduce a lipophilic substituent such as an alkyl group for the purpose of improving the solubility in a solvent.

Examples of the fluorescent dye (blue fluorescent dye) that gives blue light emission include perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
Examples of the fluorescent dye (green fluorescent dye) that gives green light emission include a quinacridone derivative and a coumarin derivative.

Examples of the fluorescent dye (yellow fluorescent dye) that gives yellow light emission include rubrene, a perimidone derivative, and the like.
Examples of the fluorescent dye (red fluorescent dye) that gives red light emission include DCM compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, and azabenzothioxanthene.

(Phosphorescent material)
The phosphorescent material refers to a material that emits light from an excited triplet state. For example, a metal complex compound having Ir, Pt, Eu, etc. is a typical example, and a material containing a metal complex is preferable as the structure of the material.

Among the metal complexes, as a phosphorescent organic metal complex that emits light via a triple term state, it is a long-periodic periodic table (hereinafter, unless otherwise specified, the term "periodic table" refers to the long-periodic table. A Werner-type complex or an organic metal complex compound containing a metal selected from Groups 7 to 11 as a central metal can be mentioned. As such a phosphorescent material, a compound represented by the formula (201) or a compound represented by the formula (205) described later is preferable, and a compound represented by the formula (201) is more preferable.

M is a metal selected from Groups 7 to 11 of the Periodic Table, and examples thereof include ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum, gold, and europium.

Ring A1 represents an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.

Ring A2 represents an aromatic heterocyclic structure which may have a substituent.

R ²⁰¹ and R ²⁰² are structures independently represented by the formula (202), and “*” indicates that they are bonded to ring A1 or ring A2. R ²⁰¹ and R ²⁰² may be the same or different, and ^{when a plurality of R 201} and R ²⁰² are present, they may be the same or different.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.

Ar ²⁰² has an aromatic hydrocarbon ring structure which may have a substituent, an aromatic heterocyclic structure which may have a substituent, or an aliphatic hydrocarbon structure which may have a substituent. Represents.

Substituents bonded to ring A1, substituents bonded to ring A2, or substituents bonded to ring A1 and substituents bonded to ring A2 may be bonded to each other to form a ring.

B ^201- L ^200- B ²⁰² represents an anionic bidentate ligand. B ²⁰¹ and B ²⁰² each independently represent a carbon atom, an oxygen atom, or a nitrogen atom, and these atoms may be atoms constituting a ring. L ²⁰⁰ represents a single bond or an atomic group constituting a bidentate ligand together with ^{B 201} and B ^202. When ^{there are a plurality of B 201-} L ^200- B ²⁰² , they may be the same or different.

i1 and i2 independently represent integers of 0 or more and 12 or less.
i3 is an integer of 0 or more up to a number substitutable for ^{Ar 202.}
j is an integer of 0 or more up to a number substitutable for ^{Ar 201.}
k1 and k2 are independently integers of 0 or more, up to a number substitutable for rings A1 and A2, respectively.
m is an integer of 1-3.

The aromatic hydrocarbon ring in ring A1 is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and the like. A fluorene ring is preferred.

As the aromatic heterocycle in ring A1, an aromatic heterocycle having 3 to 30 carbon atoms containing any of a nitrogen atom, an oxygen atom, and a sulfur atom as a heteroatom is preferable, and a furan ring and a benzofuran ring are more preferable. , Thiophene ring, benzothiophene ring.

The ring A1 is more preferably a benzene ring, a naphthalene ring, or a fluorene ring, particularly preferably a benzene ring or a fluorene ring, and most preferably a benzene ring.

The aromatic heterocycle in ring A2 is preferably an aromatic heterocycle having 3 to 30 carbon atoms and containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom.
Specifically, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, Examples include the naphthylidine ring and the phenanthridine ring.
More preferably, it is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, or a quinazoline ring.
More preferably, it is a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, or a quinazoline ring.
Most preferably, it is a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, a quinoxaline ring, or a quinazoline ring.

A preferable combination of ring A1 and ring A2 is represented by (ring A1-ring A2).
(Benzene ring-pyridine ring), (benzene ring-quinoline ring), (benzene ring-quinoxaline ring), (benzene ring-quinazoline ring), (benzene ring-imidazole ring), (benzene ring-benzothiazole ring). ..

The substituents that the rings A1 and A2 may have can be arbitrarily selected, but are preferably one or more substituents selected from the substituent group S described later.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ has an aromatic hydrocarbon ring structure which may have a substituent.
The aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms.
Specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are preferable.
More preferably, a benzene ring, a naphthalene ring, and a fluorene ring are preferable.
Most preferably, it is a benzene ring.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ^{203 is} a fluorene ring which may have a substituent, the 9-position and 9'-position of the fluorene ring have a substituent or are bonded to an adjacent structure. Is preferable.

When ^{any one of Ar 201} , Ar ²⁰² , and Ar ^{203 is} a benzene ring which may have a substituent, it is preferable that at least one benzene ring is bonded to an adjacent structure at the ortho-position or the meta-position. More preferably, at least one benzene ring is bonded to an adjacent structure at the meta position.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ has an aromatic heterocyclic structure which may have a substituent.
The aromatic heterocyclic structure is preferably an aromatic heterocycle having 3 to 30 carbon atoms and containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom.
Specifically, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxalin ring, quinazoline ring, Examples include a naphthylidine ring, a phenanthridin ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring.
More preferably, it is a pyridine ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, or a dibenzothiophene ring.

If any of Ar ²⁰¹ , Ar ²⁰² , and Ar ^{203 is} a carbazole ring which may have a substituent, the N-position of the carbazole ring may have a substituent or be bonded to an adjacent structure. preferable.

When Ar ²⁰² is an aliphatic hydrocarbon structure which may have a substituent,
The aliphatic hydrocarbon structure is an aliphatic hydrocarbon structure having a straight chain, a branched chain, or a cyclic structure.
It is preferably an aliphatic hydrocarbon having 1 or more and 24 or less carbon atoms.
More preferably, it is an aliphatic hydrocarbon having 1 or more and 12 or less carbon atoms.
More preferably, it is an aliphatic hydrocarbon having 1 or more and 8 or less carbon atoms.

i1 and i2 are independently, preferably an integer of 1 to 12, more preferably an integer of 1 to 8, and more preferably an integer of 1 to 6. Within this range, improvement in solubility and charge transportability is expected.

i3 preferably represents an integer of 0-5, more preferably an integer of 0-2, and more preferably 0 or 1.

j preferably represents an integer of 0 to 2, and is more preferably 0 or 1.

k1 and k2 preferably represent an integer of 0 to 3, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

The ^{substituents that Ar 201} , Ar ²⁰² , and Ar ²⁰³ may have can be arbitrarily selected, but are preferably one or more substituents selected from the substituent group S described later, and more preferably hydrogen. It is an atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group, and most preferably an unsubstituted (hydrogen atom).

Unless otherwise specified, the substituent is preferably a group selected from the following substituent group S.

<Substituent group S>
An alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. ..
An alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and further preferably an alkoxy group having 1 to 6 carbon atoms.
An aryloxy group, preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, further preferably an aryloxy group having 6 to 12 carbon atoms, particularly preferably 6 carbon atoms. Aryloxy group.
A heteroaryloxy group, preferably a heteroaryloxy group having 3 to 20 carbon atoms, more preferably a heteroaryloxy group having 3 to 12 carbon atoms.
-Alkylamino group, preferably an alkylamino group having 1 to 20 carbon atoms, more preferably an alkylamino group having 1 to 12 carbon atoms.
An arylamino group, preferably an arylamino group having 6 to 36 carbon atoms, more preferably an arylamino group having 6 to 24 carbon atoms.
An aralkyl group, preferably an aralkyl group having 7 to 40 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms, and further preferably an aralkyl group having 7 to 12 carbon atoms.
-Heteroaralkyl group, preferably a heteroaralkyl group having 7 to 40 carbon atoms, more preferably a heteroaralkyl group having 7 to 18 carbon atoms,
An alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, further preferably an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkenyl group having 2 to 6 carbon atoms. ..
An alkynyl group, preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 12 carbon atoms.
An aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, further preferably an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 14 carbon atoms. ..
A heteroaryl group, preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 24 carbon atoms, still more preferably a heteroaryl group having 3 to 18 carbon atoms, particularly preferably 3 to 18 carbon atoms. 14 heteroaryl groups.
An alkylsilyl group, preferably an alkylsilyl group having 1 to 20 carbon atoms, and more preferably an alkylsilyl group having 1 to 12 carbon atoms.
An arylsilyl group, preferably an arylsilyl group having 6 to 20 carbon atoms, more preferably an arylsilyl group having 6 to 14 carbon atoms.
-Alkylcarbonyl group, preferably an alkylcarbonyl group having 2 to 20 carbon atoms.
-Arylcarbonyl group, preferably an arylcarbonyl group having 7 to 20 carbon atoms.
-Hydrogen atom, deuterium atom, fluorine atom, cyano group, or -SF ₅ .

In the above group, one or more hydrogen atoms may be replaced with a fluorine atom, or one or more hydrogen atoms may be replaced with a deuterium atom.

Unless otherwise noted, aryl is an aromatic hydrocarbon and heteroaryl is an aromatic heterocycle.

(Preferable group in Substituent Group S)
Of these substituents S
Preferably, an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, and one or more hydrogen atoms of these groups are fluorine. A group replaced by an atom, a fluorine atom, a cyano group, or -SF ₅
More preferably, an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, a group in which one or more hydrogen atoms of these groups are replaced with a fluorine atom, a fluorine atom, a cyano group, or a group. , -SF ₅
More preferably, it is an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylsilyl group or an arylsilyl group.
Particularly preferred are an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, and a heteroaryl group.
Most preferably, it is an alkyl group, an arylamino group, an aralkyl group, an aryl group, or a heteroaryl group.

These substituent group S may further have a substituent selected from the substituent group S as a substituent. The preferred group, the more preferable group, the more preferable group, the particularly preferable group, and the most preferable group of the substituent which may be possessed are the same as those of the preferred group in the substituent group S and the like.

(Preferable structure of formula (201))
Among the structures represented by the formula (202) in the formula (201), an aromatic hydrocarbon in which an alkyl group or an aralkyl group is bonded to a structure having a group in which a benzene ring is linked, ring A1 or ring A2. A structure having a group or an aromatic heterocyclic group, or a structure in which benzene is bonded to ring A1 or ring A2 is preferable.

In a structure having a group in which benzene rings are linked,
Ar ²⁰¹ has a benzene ring structure, i1 is 1 to 6, and at least one of the benzene rings is bonded to an adjacent structure at the ortho-position or the meta-position.
With this structure, it is expected that the solubility is improved and the charge transportability is improved.

In a structure having an aromatic hydrocarbon group or an aromatic heterocyclic group having an alkyl group or an aralkyl group bonded to the ring A1 or the ring A2, the ring A1 or the ring A2 has an aromatic hydrocarbon group or an aromatic heterocyclic group.
Ar ²⁰¹ is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, i1 is 1 to 6, and
Ar ²⁰² is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8.
Ar ²⁰³ has a benzene ring structure, and i3 is 0 or 1.
In the case of this structure, Ar ²⁰¹ preferably has the aromatic hydrocarbon structure, more preferably a structure in which 1 to 5 benzene rings are linked, and more preferably one benzene ring.
With this structure, it is expected that the solubility is improved and the charge transportability is improved.

In the structure in which dendron is bound to ring A1 or ring A2,
Ar ²⁰¹ and Ar ²⁰² have a benzene ring structure,
Ar ²⁰³ has a biphenyl or terphenyl structure and
i1 and i2 are 1 to 6, i3 is 2, and j is 2.
With this structure, it is expected that the solubility is improved and the charge transportability is improved.

Among the structures represented by B ^201- L ^200- B ²⁰² , the structure represented by the following formula (203) or (204) is preferable.

R ²¹¹ , R ²¹² , and R ²¹³ represent substituents.

Ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent.
Ring B3 is preferably a pyridine ring.

The phosphorescent material represented by the formula (201) is not particularly limited, and specific examples thereof include the following structures.
In addition, Me means a methyl group and Ph means a phenyl group.

Here, the compound represented by the following formula (205) will be described.

In formula (205), M ² represents a metal and T represents a carbon or nitrogen atom. R ^{92 to} R ⁹⁵ each independently represent a substituent. However, when T is a nitrogen atom, R ⁹⁴ and R ⁹⁵ do not exist.

In formula (205), M ² represents a metal. Specific examples include metals selected from Groups 7 to 11 of the Periodic Table. Of these, ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum or gold are preferable, and divalent metals such as platinum and palladium are particularly preferable.

Further, in the formula (205), R ⁹² and R ⁹³ are independently hydrogen atom, halogen atom, alkyl group, aralkyl group, alkenyl group, cyano group, amino group, acyl group, alkoxycarbonyl group, carboxyl group, respectively. Represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group.

Further, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ independently represent substituents represented by the same examples as ^{R 92} and R ^{93, respectively.} Further, when T is a nitrogen atom, R ⁹⁴ or R ⁹⁵ that directly bonds to the T does not exist.

Further, R ^{92 to} R ⁹⁵ may further have a substituent. As the substituent, the above-mentioned substituents listed as ^{R 92} and R ^{93 can be used.} Further, ^{any two or more groups of R 92 to} R ⁹⁵ may be connected to each other to form a ring.

(Molecular weight)
The molecular weight of the phosphorescent material is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less. The molecular weight of the phosphorescent material is usually 800 or more, preferably 1000 or more, and more preferably 1200 or more. Within this molecular weight range, it is considered that the phosphorescent materials do not aggregate with each other and are uniformly mixed with the charge transport material to obtain a light emitting layer having high luminous efficiency.

The molecular weight of the phosphorescent material is high in Tg, melting point, decomposition temperature, etc., and the heat resistance of the phosphorescent material and the formed light emitting layer is excellent, and the film quality due to gas generation, recrystallization, molecular migration, etc. It is preferable that it is large in that it is unlikely that a decrease in the concentration of impurities or an increase in the concentration of impurities due to thermal decomposition of the material will occur. On the other hand, the molecular weight of the phosphorescent material is preferably small in that the organic compound can be easily purified.

[3] Host Material The composition for an organic electroluminescent device of the present invention preferably contains a host material.

The host material of the light emitting layer is a material having a skeleton excellent in charge transportability, and is preferably selected from an electron transporting material, a hole transporting material, and a bipolar material capable of transporting both electrons and holes.

Specific examples of the skeleton having excellent charge transport properties include an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, a porphyrin structure, a thiophene structure, and a benzylphenyl structure. Examples thereof include a fluorene structure, a quinacridone structure, a triphenylene structure, a carbazole structure, a pyrene structure, an anthracene structure, a phenanthrene structure, a quinoline structure, a pyridine structure, a pyrimidine structure, a triazine structure, an oxadiazole structure or an imidazole structure.

As the electron transporting material, a compound having a pyridine structure, a pyrimidine structure, and / or a triazine structure, which is excellent in electron transportability and has a relatively stable structure, is more preferable, and a compound having a pyrimidine structure and / or a triazine structure is further preferable. preferable.

The hole transporting material is a compound having a structure excellent in hole transporting property, and among the skeletons having excellent hole transporting property, a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure or a pyrene structure. Is preferable as a structure having excellent hole transportability, and a carbazole structure, a dibenzofuran structure or a triarylamine structure is more preferable.

The host material of the light emitting layer preferably has a condensed ring structure of 3 or more rings, and is further preferably a compound having 2 or more condensed ring structures of 3 or more rings or a compound having at least one condensed ring structure of 5 or more rings. preferable. By using these compounds, the rigidity of the molecule is increased, and the effect of suppressing the degree of molecular motion in response to heat can be easily obtained. Further, it is preferable that the condensed ring having 3 or more rings and the condensed ring having 5 or more rings have an aromatic hydrocarbon ring or an aromatic heterocycle in terms of charge transportability and material durability.

Specific examples of the fused ring structure having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofurene structure, indenofluorene structure, and indolofluorene structure. Examples thereof include a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure, and a dibenzothiophene structure.

From the viewpoint of charge transportability and solubility, at least one selected from the group consisting of phenanthrene structure, fluorene structure, indenofluorene structure, carbazole structure, indenocarbazole structure, indolocarbazole structure, dibenzofuran structure and dibenzothiophene structure is selected. Preferably, a carbazole structure or an indolocarbazole structure is more preferable from the viewpoint of durability against charge.

In the present invention, from the viewpoint of durability against electric charge of the organic electroluminescent element, at least one of the host materials of the light emitting layer is preferably a material having a pyrimidine skeleton or a triazine skeleton.

The host material of the light emitting layer is preferably a polymer material from the viewpoint of excellent flexibility. A light emitting layer formed by using a material having excellent flexibility is preferable as a light emitting layer of an organic electroluminescent element formed on a flexible substrate. When the host material contained in the light emitting layer is a polymer material, the molecular weight is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less, and more preferably 10,000 or more. It is 100,000 or less.

The host material of the light emitting layer is a small molecule from the viewpoints of ease of synthesis and purification, ease of designing electron transport performance and hole transport performance, and ease of viscosity adjustment when dissolved in a solvent. Is preferable. When the host material contained in the light emitting layer is a low molecular weight material, the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,. It is 000 or less, usually 300 or more, preferably 350 or more, and more preferably 400 or more.

[4] Other Components The composition for an organic electroluminescent device of the present invention may contain various other solvents, if necessary, in addition to the above-mentioned solvent and light-emitting material. Examples of such other solvents include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide and the like.

Further, the composition for an organic electroluminescent device of the present invention may contain various additives such as a leveling agent and a defoaming agent.
Further, when laminating two or more layers by a wet film forming method, in order to prevent these layers from being compatible with each other, a photocurable resin or a thermosetting resin is used for the purpose of curing and insolubilizing after film formation. Can also be contained.

[5] Material concentration and compounding ratio in composition for organic electric field light emitting element The aromatic compound of the present invention, light emitting material and components (leveling agent, etc.) that can be added as needed in the composition for organic electric field light emitting element, etc. The solid content concentration of is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and most preferably 1% by mass or more. It is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and most preferably 20% by mass or less. When the concentration is in this range, a thin film having a desired film thickness can be easily formed with a uniform thickness, which is preferable.

Further, in the composition for an organic electroluminescent element of the present invention, the mass mixing ratio of the light emitting material / aromatic compound is usually 0.1 / 99.9 or more, more preferably 0.5 / 99.5 or more. It is more preferably 1/99 or more, most preferably 2/98 or more, usually 50/50 or less, more preferably 40/60 or less, still more preferably 30/70 or less. , Most preferably 20/80 or less. If this ratio falls below the lower limit or exceeds the upper limit, the luminous efficiency may be significantly reduced.

[6] Method for Preparing Composition for Organic Electroluminescent Element The composition for an organic electroluminescent element of the present invention comprises the aromatic compound of the present invention, the above-mentioned light emitting material if necessary, and leveling that can be added if necessary. It is prepared by dissolving a solute consisting of various additives such as an agent and an antifoaming agent in an appropriate solvent.

In order to shorten the time required for the dissolution step and to keep the solute concentration in the composition uniform, the solute is usually dissolved while stirring the liquid. The melting step may be carried out at room temperature, but if the melting rate is slow, it can be melted by heating. After the dissolution step is completed, if necessary, it may go through a filtration step such as filtering.

[7] Properties, physical properties, etc. of the composition for an organic electroluminescent device (moisture concentration)
When the organic electroluminescent device is produced by forming a layer by a wet film forming method using the composition for an organic electroluminescent device of the present invention, a film formed when water is present in the composition for the organic electroluminescent device to be used. It is preferable that the water content in the composition for the organic electroluminescent device of the present invention is as small as possible because water is mixed in and the uniformity of the film is impaired. Further, in general, many materials such as cathodes that are significantly deteriorated by moisture are used in organic electroluminescent devices. Therefore, when moisture is present in the composition for an organic electroluminescent device, moisture is present in the dried film. It is not preferable because it may remain and deteriorate the characteristics of the device.

Specifically, the amount of water contained in the composition for an organic electroluminescent element of the present invention is usually 1% by mass or less, preferably 0.1% by mass or less, and more preferably 0.01% by mass or less.

As a method for measuring the water concentration in the composition for an organic electric field light emitting element, the method described in the Japanese Industrial Standards "Moisture measurement method for chemical products" (JIS K0068: 2001) is preferable, and for example, the Karl Fischer reagent method (JIS K0211). It can be analyzed by -1348) and the like.

(Uniformity)
The composition for an organic electroluminescent element of the present invention is preferably a uniform liquid at room temperature in order to improve stability in a wet film forming process, for example, ejection stability from a nozzle in an inkjet film forming method. .. The uniform liquid at room temperature means that the composition is a liquid composed of a uniform phase and does not contain a particle component having a particle size of 0.1 μm or more in the composition.

(Physical characteristics)
When the viscosity of the composition for an organic electroluminescent element of the present invention is extremely low, for example, uneven coating surface due to excessive liquid film flow in the film forming process, nozzle ejection failure in inkjet film forming, and the like are likely to occur. When the viscosity of the composition for an organic electroluminescent element of the present invention is extremely high, nozzle clogging or the like in inkjet film formation is likely to occur. Therefore, the viscosity of the composition of the present invention at 25 ° C. is usually 2 mPa · s or more, preferably 3 mPa · s or more, more preferably 5 mPa · s or more, and usually 1000 mPa · s or less, preferably 100 mPa · s or less. , More preferably 50 mPa · s or less.

Further, when the surface tension of the composition for an organic electric field light emitting element of the present invention is high, the wettability of the film-forming liquid with respect to the substrate is lowered, the leveling property of the liquid film is poor, and the film-forming surface is disturbed during drying. The surface tension of the composition of the present invention at 20 ° C. is usually less than 50 mN / m, preferably less than 40 mN / m, because problems such as facilitation may occur.

Further, when the vapor pressure of the composition for an organic electroluminescent element of the present invention is high, problems such as a change in solute concentration due to evaporation of the solvent may easily occur. Therefore, the vapor pressure of the composition of the present invention at 25 ° C. is usually 50 mmHg or less, preferably 10 mmHg or less, and more preferably 1 mmHg or less.

<Organic electroluminescent device>
The organic electroluminescent element of the present invention has an anode and a cathode on a substrate and has an organic layer between the anode and the cathode, and the organic layer contains a material for an organic electroluminescent element. The material for an organic electroluminescent element contains the aromatic compound of the present invention.

The layer containing the aromatic compound is preferably formed by using the material for an organic electroluminescent element or the composition for an organic electroluminescent element of the present invention.
Further, the layer containing the material for the organic electroluminescent device is preferably a light emitting layer.

Further, it is preferable that the layer containing the aromatic compound is doped with an organometallic complex. As the organometallic complex, those exemplified as the light emitting material can be used.

Further, the aromatic compound of the present invention has a large energy gap (difference between HOMO and LUMO), a high excited triplet level (T1), and has high hole transportability, so that it may be contained in the electron blocking layer. preferable. Hereinafter, the layer structure of the organic electroluminescent device of the present invention, a general method for forming the same, and the like will be described with reference to FIG.

FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescent device of the present invention. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, and 8 is an electron injection layer. 9 represents a cathode and 10 represents an organic electroluminescent element.

In the present invention, the wet film forming method includes, for example, a spin coating method, a dip coating method, a die coating method, a bar coating method, a blade coating method, a roll coating method, a spray coating method, a capillary coating method, an inkjet method, and screen printing. A wet film forming method such as a method, a gravure printing method, or a flexographic printing method. Among these film forming methods, a spin coating method, a spray coating method, and an inkjet method are preferable. This is because the spin coating method, the spray coating method, and the inkjet method are suitable for the liquid properties peculiar to the coating composition used for the organic electroluminescent device.

[1] Substrate The substrate 1 serves as a support for an organic electroluminescent element, and a quartz or glass plate, a metal plate, a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to the gas barrier property. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air passing through the substrate. Therefore, a method of ensuring gas barrier properties by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also one of the preferable methods.

[2] Anode The anode 2 plays a role of injecting holes into the layer on the light emitting layer side.
The anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or carbon black. It is composed of conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline.

The anode 2 is usually formed by a sputtering method, a vacuum vapor deposition method, or the like. Further, when the anode 2 is formed by using metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., an appropriate binder resin solution is used. It is also possible to form the anode 2 by dispersing it in the substrate 1 and applying it on the substrate 1. Further, in the case of a conductive polymer, a thin film can be formed directly on the substrate 1 by electrolytic polymerization, or an anode 2 can be formed by applying the conductive polymer on the substrate 1 (Appl. Phys. Lett). , Vol. 60, p. 2711, 1992).

The anode 2 usually has a single-layer structure, but it is also possible to have a laminated structure made of a plurality of materials if desired.

The thickness of the anode 2 depends on the required transparency. When transparency is required, the transmittance of visible light is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably about 500 nm or less. When it is opaque, the thickness of the anode 2 is arbitrary, and the thickness of the anode 2 may be the same as the thickness of the substrate 1. Further, it is also possible to laminate different conductive materials on the above-mentioned anode 2.

The surface of the anode 2 is treated with ultraviolet rays (UV) / ozone, oxygen plasma treatment, or argon plasma treatment for the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property. It is preferable to do so.

[3] Hole Injection Layer The hole injection layer 3 is a layer for transporting holes from the anode 2 to the light emitting layer 5, and is usually formed on the anode 2.

The method for forming the hole injection layer 3 of the present invention may be a vacuum vapor deposition method or a wet film formation method, and is not particularly limited. However, the hole injection layer 3 is formed by the wet film formation method from the viewpoint of reducing dark spots. Is preferable.

The film thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

(Formation of hole injection layer by wet film formation method)
When the hole injection layer 3 is formed by the wet film formation method, usually, the material constituting the hole injection layer 3 is mixed with an appropriate solvent (hole injection layer solvent) to form a film-forming composition (the hole injection layer solvent). A composition for forming a hole injection layer) is prepared, and this composition for forming a hole injection layer is applied onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer 3 by an appropriate method. The hole injection layer 3 is formed by forming a film and drying it.

(Hole transporting compound)
The composition for forming a hole injection layer usually contains a hole transporting compound and a solvent as a constituent material of the hole injection layer.

The hole-transporting compound is a polymer compound such as a polymer as long as it is a compound having a hole-transporting property that is usually used for the hole injection layer of an organic electric field light emitting element. It may be a low molecular weight compound, but it is preferably a high molecular weight compound.

As the hole transporting compound, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3. Examples of hole-transporting compounds include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl derivatives, compounds in which a tertiary amine is linked with a fluorene group, hydrazone derivatives, silazane derivatives, and silanamin. Examples thereof include derivatives, phosphamine derivatives, quinacridone derivatives, polyaniline derivatives, polypyrrole derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polyquinolin derivatives, polyquinoxalin derivatives, carbon and the like.

In the present invention, the derivative includes, for example, an aromatic amine derivative itself and a compound having an aromatic amine as a main skeleton, and even if it is a polymer, it is simply a derivative. It may be a metric.

The hole-transporting compound used as the material of the hole injection layer 3 may contain any one of such compounds alone, or may contain two or more of them. When two or more kinds of hole-transporting compounds are contained, the combination thereof is arbitrary, but one or more kinds of aromatic tertiary amine polymer compounds and one or two kinds of other hole-transporting compounds are contained. It is preferable to use the above in combination.

Among the above-exemplified examples, aromatic amine compounds are preferable, and aromatic tertiary amine compounds are particularly preferable, from the viewpoint of amorphousness and visible light transmittance. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and also includes a compound having a group derived from the aromatic tertiary amine.

The type of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, polymer compounds having a weight average molecular weight of 1000 or more and 1000,000 or less (polymerized compounds having a series of repeating units) are further added. preferable. A preferable example of the aromatic tertiary amine polymer compound is a polymer compound having a repeating unit represented by the following formula (I).

In formula (I), Ar ⁵¹ and Ar ⁵² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. . Ar ^{53 to} Ar ⁵⁵ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Y represents the following. It represents a linking group selected from the linking group group. Further, of Ar ^{51 to} Ar ⁵⁵ , two groups bonded to the same N atom may be bonded to each other to form a ring.)

(In each of the above formulas, Ar ^{56 to} Ar ⁶⁶ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. R ³¹ and R ³² each independently represent a hydrogen atom or any substituent.)

The aromatic hydrocarbon groups and aromatic heterocyclic groups of Ar ^{56 to} Ar ⁶⁶ include benzene rings, naphthalene rings, phenanthrene rings, and thiophenes from the viewpoints of solubility, heat resistance, and hole injection / transportability of polymer compounds. A group derived from a ring or a pyridine ring is preferable, and a group derived from a benzene ring or a naphthalene ring is more preferable.

The aromatic hydrocarbon groups and aromatic heterocyclic groups of Ar ^{56 to} Ar ^{66 may further have a substituent.} The molecular weight of the substituent is usually 400 or less, particularly preferably about 250 or less. As the substituent, an alkyl group, an alkenyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like are preferable.

When R ³¹ and R ³² are arbitrary substituents, examples of the substituent include an alkyl group, an alkenyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like. ..

Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (I) include those described in International Publication No. 2005/089024.

Further, as the hole transporting compound, a conductive polymer (PEDOT / PSS) obtained by polymerizing 3,4-ethylenedioxythiophene, which is a derivative of polythiophene, in high-molecular-weight polystyrene sulfonic acid. Is also preferable. Further, the end of this polymer may be capped with methacrylate or the like.

The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in terms of film thickness uniformity. Is 0.1% by mass or more, more preferably 0.5% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. If this concentration is too large, uneven film thickness may occur, and if it is too small, defects may occur in the formed hole injection layer.

(Electron accepting compound)
The composition for forming a hole injection layer preferably contains an electron-accepting compound as a constituent material of the hole injection layer. Here, the electron-accepting compound is preferably a compound having an oxidizing power and having an ability to accept one electron from the above-mentioned hole-transporting compound, and specifically, a compound having an electron affinity of 4 eV or more is preferable. , A compound having an electron affinity of 5 eV or more is more preferable.

Such an electron-accepting compound includes, for example, a triarylboron compound, a metal halide, a Lewis acid, an organic acid, an onium salt, a salt of an arylamine and a metal halide, and a salt of an arylamine and a Lewis acid. One or more compounds selected from the group may be mentioned.

Specifically, onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pendafluorophenyl) borate, triphenylsulfonium tetrafluoroborate (International Publication No. 2005/089024); chloride. Iron (III) (Japanese Patent Laid-Open No. 11-251067), high valence inorganic compounds such as ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene, tris (pendafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-313665) Aromatic boron compounds such as; fullerene derivatives; iodine; sulfonic acid ions such as polystyrene sulfonic acid ion, alkylbenzene sulfonic acid ion, and Drosophila sulfonic acid ion.

These electron-accepting compounds can improve the conductivity of the hole-injected layer by oxidizing the hole-transporting compound.

The content of the electron-accepting compound in the hole-injecting layer or the composition for forming the hole-injecting layer with respect to the hole-transporting compound is usually 0.1 mol% or more, preferably 1 mol% or more, and is usually It is 100 mol% or less, preferably 40 mol% or less.

(Other constituent materials)
The material of the hole injection layer may further contain other components in addition to the above-mentioned hole transporting compound and electron accepting compound as long as the effects of the present invention are not significantly impaired. Examples of other components include various light-emitting materials, electron-transporting compounds, binder resins, and coatability improvers. As the other components, only one type may be used, or two or more types may be used in any combination and ratio.

(solvent)
It is preferable that at least one of the solvents of the composition for forming the hole injection layer used in the wet film forming method is a compound capable of dissolving the constituent material of the hole injection layer described above. The boiling point of this solvent is usually 110 ° C. or higher, preferably 140 ° C. or higher, more preferably 200 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower. If the boiling point of the solvent is too low, the drying rate may be too fast and the film quality may deteriorate. Further, if the boiling point of the solvent is too high, it is necessary to raise the temperature of the drying step, which may adversely affect other layers and substrates.

Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents and the like.

Examples of the ether-based solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , Fenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers.

Examples of the ester-based solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-iropropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. Can be mentioned.

Examples of the amide-based solvent include N, N-dimethylformamide, N, N-dimethylacetamide and the like.

In addition, dimethyl sulfoxide, etc. can also be used.
Only one of these solvents may be used, or two or more of these solvents may be used in any combination and ratio.

(Film formation method)
After preparing the composition for forming the hole injection layer, this composition is applied and formed on the layer corresponding to the lower layer of the hole injection layer 3 (usually, the anode 2) by wet film formation, and dried. The hole injection layer 3 is formed.

The temperature in the film forming step is preferably 10 ° C. or higher, preferably 50 ° C. or lower, in order to prevent the film from being damaged due to the formation of crystals in the composition.

The relative humidity in the film forming step is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.01 ppm or more and usually 80% or less.

After the film formation, the film of the composition for forming a hole injection layer is usually dried by heating or the like. Examples of heating means used in the heating step include clean ovens, hot plates, infrared rays, halogen heaters, microwave irradiation and the like. Above all, a clean oven and a hot plate are preferable in order to evenly apply heat to the entire film.

The heating temperature in the heating step is preferably a temperature equal to or higher than the boiling point of the solvent used in the composition for forming a hole injection layer, as long as the effects of the present invention are not significantly impaired. Further, in the case of a mixed solvent containing two or more kinds of solvents used for the hole injection layer, it is preferable that at least one kind is heated at a temperature equal to or higher than the boiling point of the solvent. Considering the boiling point elevation of the solvent, it is preferable to heat at 120 ° C. or higher and 410 ° C. or lower in the heating step.

In the heating step, if the heating temperature is equal to or higher than the boiling point of the solvent for forming the hole injection layer and the coating film is not sufficiently insolubilized, the heating time is not limited, but is preferably 10 seconds or longer, usually 180. Less than a minute. If the heating time is too long, the components of other layers tend to diffuse, and if it is too short, the hole injection layer tends to become inhomogeneous. The heating may be performed in two steps.

(Formation of hole injection layer by vacuum deposition method)
When the hole injection layer 3 is formed by the vacuum vapor deposition method, one or more of the constituent materials of the hole injection layer 3 (the above-mentioned hole transporting compound, electron accepting compound, etc.) are placed in a vacuum vessel. Put it in the crucible installed in (2 if you use two or more materials, put it in each crucible), ^{exhaust the inside of the vacuum vessel to about 10 -4} Pa with an appropriate vacuum pump, and then heat the crucible (2). When using more than one kind of material, heat each crucible), control the amount of evaporation to evaporate (when using two or more kinds of materials, control the amount of evaporation independently to evaporate), and use the crucible. The hole injection layer 3 is formed on the anode 2 of the substrates placed facing each other. When two or more kinds of materials are used, a mixture thereof can be put in a crucible and heated and evaporated to form the hole injection layer 3.

The degree of vacuum during vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 × 10 ^-6 Torr (0.13 × 10 ^-4 Pa) or more, and usually 9.0 × 10 ^-6 Torr. It is (12.0 × 10 ^-4 Pa) or less. The vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 Å / sec or more and usually 5.0 Å / sec or less. The film formation temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher, preferably 50 ° C. or lower.

[4] Hole Transport Layer The method for forming the hole transport layer 4 of the present invention may be a vacuum vapor deposition method or a wet film deposition method, and there is no particular limitation, but the hole transport layer 4 is wet-treated from the viewpoint of reducing dark spots. It is preferably formed by a film forming method.

The hole transport layer 4 can be formed on the hole injection layer 3 when there is a hole injection layer, and on the anode 2 when there is no hole injection layer 3. Further, the organic electroluminescent device of the present invention may have a configuration in which the hole transport layer is omitted.

As the material for forming the hole transport layer 4, it is preferable that the material has high hole transportability and can efficiently transport the injected holes. Therefore, it is preferable that the ionization potential is small, the transparency is high with respect to visible light, the hole mobility is large, the stability is excellent, and impurities that become traps are less likely to be generated during production or use. Further, in many cases, since the hole transport layer 4 is in contact with the light emitting layer 5, it does not quench the light emitted from the light emitting layer 5 or form an exciplex with the light emitting layer 5 to reduce the efficiency. Is preferable.

The material of such a hole transport layer 4 may be any material conventionally used as a constituent material of the hole transport layer, and for example, the hole transport property used in the hole injection layer 3 described above. Examples thereof include those exemplified. In addition, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, silol derivatives, oligothiophene derivatives, condensed polycyclic fragrances. Group derivatives, metal complexes and the like can be mentioned.

Further, for example, a polyvinylcarbazole derivative, a polyarylamine derivative, a polyvinyltriphenylamine derivative, a polyfluorene derivative, a polyarylene derivative, a polyarylene ether sulfone derivative containing tetraphenylbenzidine, a polyarylene vinylene derivative, a polysiloxane derivative, and polythiophene. Derivatives, poly (p-phenylene vinylene) derivatives and the like can be mentioned. These may be any of alternating copolymers, random polymers, block polymers or graft copolymers. Further, it may be a polymer having a branch in the main chain and having three or more terminal portions, or a so-called dendrimer.

Of these, polyarylamine derivatives and polyarylene derivatives are preferable.
As the polyarylamine derivative, a polymer containing a repeating unit represented by the following formula (II) is preferable. In particular, a polymer composed of repeating units represented by the following formula (II) is preferable, and in this case, Ar ^a or Ar ^b may be different in each repeating unit.

(In formula (II), Ar ^a and Ar ^b each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.)

Examples of the aromatic hydrocarbon group which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrycene ring, a triphenylene ring, and an acenaphthene. Examples thereof include groups derived from a 6-membered monocyclic ring or a 2 to 5 fused ring such as a ring, a fluorene ring, and a fluorene ring, and a group in which two or more rings are directly linked by a direct bond.

Examples of the aromatic heterocyclic group which may have a substituent include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring. , Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrrole ring, Flofuran ring, Thienofuran ring, Benzisoxazole ring, Benzentithiazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Pyridazine A single 5- or 6-membered ring such as a ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazolin ring, a quinazolinone ring, or an azulene ring. Examples thereof include a group derived from a ring or a 2-4 condensed ring and a group formed by directly bonding two or more rings thereof.

From the viewpoint of solubility and heat resistance, Ar ^a and Ar ^b are independently composed of a group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring. A group derived from the selected ring or a group in which two or more benzene rings are linked (for example, a biphenyl group or a terphenyl group) is preferable. Of these, a group derived from a benzene ring (phenyl group), a group formed by linking two benzene rings (biphenyl group), and a group derived from a fluorene ring (fluorenyl group) are preferable.

The ^{substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar a} and Ar ^b may have include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group and a dialkyl group. Examples thereof include an amino group, a diarylamino group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a syroxy group, a cyano group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

As the polyarylene derivative, an arylene group such as an aromatic hydrocarbon group or an aromatic heterocyclic group, which may have a substituent exemplified as ^{Ar a} or Ar ^b in the above formula (II), is used as a repeating unit thereof. Examples thereof include polymers having.

As the polyarylene derivative, a polymer having a repeating unit having the following formula (III-1) and / or the following formula (III-2) is preferable.

(In formula (III-1), ^Ra , R ^b , R ^c and R ^d are independently alkyl groups, alkoxy groups, phenylalkyl groups, phenylalkoxy groups, phenyl groups, phenoxy groups, alkylphenyl groups, respectively. Represents an alkoxyphenyl group, an alkylcarbonyl group, an alkoxycarbonyl group or a carboxy group. T and s independently represent an integer of 0 to 3. When t or s is 2 or more, a plurality of substances contained in one molecule. R ^a or R ^b may be the same ^{or different, and adjacent Ra} or R ^b may form a ring.)

(In formula (III-2), ^Re and R ^{f are independently synonymous with Ra} , R ^b , R ^c or R ^d in the above formula (III-1), respectively. R and u are synonymous with each other. independently, the case of 2 or more .r or u represents an integer of 0 to 3, a plurality of R ^e and R ^f contained in one molecule may be the same or different and adjacent R ^e or Rings may be formed between R ^fs. X represents an atom or a group of atoms constituting a 5-membered ring or a 6-membered ring.)

Specific examples of X include an oxygen atom, a boron atom which may have a substituent, a nitrogen atom which may have a substituent, a silicon atom which may have a substituent, and a substituent. It is a phosphorus atom which may have a substituent, a sulfur atom which may have a substituent, a carbon atom which may have a substituent, or a group formed by bonding these.

Further, the polyarylene derivative has a repeating unit represented by the following formula (III-3) in addition to the repeating unit composed of the above formula (III-1) and / or the above formula (III-2). Is preferable.

(In formula (III-3), Ar ^{c to} Ar ⁱ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. V and w represent, respectively. Independently represents 0 or 1)

Specific examples of Ar ^{c to} Ar ⁱ are the same as those of ^{Ar a} and Ar ^b in the above formula (II).

Specific examples of the above formulas (III-1) to (III-3) and specific examples of polyarylene derivatives include those described in Japanese Patent Application Laid-Open No. 2008-98619.

When the hole transport layer 4 is formed by the wet film formation method, the composition for forming the hole transport layer is prepared in the same manner as in the formation of the hole injection layer 3, then the wet film formation and then heat drying. ..

The composition for forming a hole transport layer contains a solvent in addition to the above-mentioned hole transport compound. The solvent used is the same as that used in the composition for forming the hole injection layer. Further, the film forming conditions, the heat drying conditions, and the like are the same as in the case of forming the hole injection layer 3.

Also when the hole transport layer is formed by the vacuum vapor deposition method, the film forming conditions and the like are the same as in the case of forming the hole injection layer 3.

In addition to the hole transporting compound, the hole transporting layer 4 may contain various light emitting materials, an electron transporting compound, a binder resin, a coating property improving agent, and the like.

Further, the hole transport layer 4 may be a layer formed by cross-linking a cross-linking compound. The crosslinkable compound is a compound having a crosslinkable group, and forms a network polymer compound by crosslinking.

Examples of this crosslinkable group are groups derived from cyclic ethers such as oxetane and epoxy; groups derived from unsaturated double bonds such as vinyl group, trifluorovinyl group, styryl group, acrylic group, methacryloyl and cinnamoyl; benzo. Examples include groups derived from cyclobutene.

The crosslinkable compound may be a monomer, an oligomer, or a polymer. The crosslinkable compound may have only one kind, or may have two or more kinds in any combination and ratio.

As the crosslinkable compound, it is preferable to use a hole transporting compound having a crosslinkable group. Examples of the hole transporting compound include those exemplified above, and examples of the crosslinkable compound include those in which a crosslinkable group is bonded to the main chain or side chain of these hole transporting compounds. Be done. In particular, the crosslinkable group is preferably bonded to the main chain via a linking group such as an alkylene group. Further, the hole transporting compound is preferably a polymer containing a repeating unit having a crosslinkable group, and the crosslinkable group is described in the above formulas (II) and (III-1) to (III-3). Is preferably a polymer having repeating units bonded directly or via a linking group.

As the crosslinkable compound, it is preferable to use a hole transporting compound having a crosslinkable group. Examples of hole-transporting compounds include nitrogen-containing aromatic compound derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives, phthalocyanine derivatives, and porphyrin derivatives; triphenylamine derivatives. Examples thereof include silol derivatives; oligothiophene derivatives; condensed polycyclic aromatic derivatives; metal complexes and the like.

Among them, nitrogen-containing aromatic derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives and carbazole derivatives; triphenylamine derivatives; silol derivatives; condensed polycyclic aromatic derivatives; metal complexes and the like. Preferred, especially triphenylamine derivatives are more preferred.

In order to crosslink the crosslinkable compound to form the hole transport layer 4, usually, a composition for forming a hole transport layer in which the crosslinkable compound is dissolved or dispersed in a solvent is prepared, and a film is formed by wet film formation. To bridge.

The composition for forming a hole transport layer may contain an additive that promotes the cross-linking reaction in addition to the cross-linking compound. Examples of additives that promote the cross-linking reaction include polymerization initiators and polymerization accelerators such as alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds, and onium salts; condensed polycyclic hydrocarbons; Examples thereof include a porphyrin compound; a photosensitizer such as a diarylketone compound.

Further, the composition for forming a hole transport layer may contain a coating property improving agent such as a leveling agent and a defoaming agent; an electron accepting compound; a binder resin and the like.

The composition for forming a hole transport layer usually contains a crosslinkable compound in an amount of 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The composition for forming a hole transport layer usually contains a crosslinkable compound in an amount of 50% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.

A composition for forming a hole transport layer containing a crosslinkable compound at such a concentration is formed on a lower layer (usually a hole injection layer 3), and then the crosslinkable compound is heated and / or irradiated with electromagnetic energy such as light. Is crosslinked to form a network polymer compound.

The conditions such as temperature and humidity at the time of film formation are the same as those at the time of wet film formation of the hole injection layer 3. The method of heating after film formation is not particularly limited. The heating temperature condition is usually 120 ° C. or higher, preferably 400 ° C. or lower.

The heating time is usually 1 minute or more, preferably 24 hours or less. The heating means is not particularly limited, but means such as placing a laminate having a film-formed layer on a hot plate or heating in an oven are used. For example, conditions such as heating on a hot plate at 120 ° C. or higher for 1 minute or longer can be used.

When irradiating with electromagnetic energy such as light, a method of irradiating by directly using an ultraviolet / visible / infrared light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, or an infrared lamp, or the above-mentioned light source is built in. Examples thereof include a method of irradiating using a mask aligner and a conveyor type light irradiating device. Examples of electromagnetic energy irradiation other than light include a method of irradiating using a device that irradiates microwaves generated by a magnetron, a so-called microwave oven.

The irradiation time is preferably set to conditions necessary for reducing the solubility of the membrane, but is usually 0.1 seconds or longer, preferably 10 hours or shorter.

Heating and irradiation with electromagnetic energy such as light may be performed individually or in combination, respectively. When combined, the order of implementation is not particularly limited.

The film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 100 nm or less.

[5] Light-emitting layer A light-emitting layer 5 is provided on the hole injection layer 3 or, when the hole transport layer 4 is provided, on the hole transport layer 4. The light emitting layer 5 is a layer that is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between the electrodes to which an electric field is applied, and becomes a main light emitting source.

(Material of light emitting layer)
The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) as a constituent material thereof, and preferably a compound having a hole transporting property (hole transporting compound) or an electron transporting property. Contains a compound (electron-transporting compound) having the properties of. A light emitting material may be used as the dopant material, and a hole transporting compound, an electron transporting compound, or the like may be used as the host material.

The light emitting material is not particularly limited, and a substance that emits light at a desired light emitting wavelength and has good luminous efficiency may be used, but in the present invention, the above-mentioned light emitting material is preferably used. On the other hand, it is preferable to use the aromatic compound of the present invention as the host material, particularly the hole transporting compound.

In particular, it is preferable that the light emitting layer of the organic electroluminescent element of the present invention is formed by a wet film forming method using the composition for an organic electroluminescent element of the present invention.

Further, the light emitting layer 5 may contain other components as long as the effects of the present invention are not significantly impaired. When the light emitting layer 5 is formed by the wet film forming method, it is preferable to use a material having a low molecular weight (molecular weight: usually 10,000 or less, preferably 5000 or less).

<Formation of light emitting layer>
When the light emitting layer 5 is formed by the wet film forming method, the material used for the light emitting layer is dissolved in an appropriate solvent to form a light emitting layer composition (when the aromatic compound of the present invention is contained, the composition for an organic electroluminescent element). The product) is prepared and formed by forming a film using it.

The solvent for the light emitting layer to be contained in the composition for forming the light emitting layer for forming the light emitting layer 5 by the wet film forming method has been described as the solvent contained in the composition for the organic electroluminescent element of the present invention. The same is true.

The solid content concentration of the light emitting material, the charge transporting compound, etc. in the light emitting layer forming composition is usually 0.01% by mass or more and usually 70% by mass or less. If this concentration is too large, uneven film thickness may occur, and if it is too small, defects may occur in the film.

After the composition for forming a light emitting layer is wet-formed, the obtained coating film is dried and the solvent is removed to form a light emitting layer. Specifically, it is the same as the method described in the formation of the hole injection layer. The method of the wet film forming method is not limited as long as the effect of the present invention is not significantly impaired, and any of the above-mentioned methods can be used.

The film thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually in the range of 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. If the film thickness of the light emitting layer 5 is too thin, defects may occur in the film, and if it is too thick, the drive voltage may increase.

[6] Hole Blocking Layer In the organic electroluminescent device of the present invention, it is preferable to provide a hole blocking layer 6 between the light emitting layer 5 and the electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.

The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Has.

The physical properties required for the material constituting the hole blocking layer 6 are high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T1). Is high.

Examples of the material of the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanorat) aluminum, and the like. Mixed ligand complexes of, bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolilato) aluminum dinuclear metal complexes and other metal complexes, distyrylbiphenyl derivatives and the like. Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No. 11-242996), 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (Japanese Patent Laid-Open No. 7) 4-1759), phenylintroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297), and the like. Further, a compound having at least one pyridine ring in which the 2, 4 and 6 positions are substituted as described in WO 2005/022962 is also preferable as a material for the hole blocking layer 6.

As the material of the hole blocking layer 6, only one kind may be used, or two or more kinds may be used in any combination and ratio.

There is no limitation on the method of forming the hole blocking layer 6. Therefore, the hole blocking layer 6 can be formed by a wet film deposition method, a vacuum vapor deposition method, or other methods.

The film thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. be.

Further, a hole relaxation layer may be provided instead of the hole blocking layer.

[7] Electron transport layer An electron transport layer 7 may be provided between the light emitting layer 5 and the electron injection layer 8 described later.
The electron transport layer 7 is provided for the purpose of further improving the luminous efficiency of the element, and efficiently transports the electrons injected from the cathode 9 in the direction of the light emitting layer 5 between the electrodes to which an electric field is applied. It is formed by a compound that can.

The electron-transporting compound used in the electron-transporting layer 7 usually has high electron-injection efficiency from the cathode 9 or the electron-injection layer 8 and has high electron mobility to efficiently transport the injected electrons. Use a compound that can. Examples of the compound satisfying such conditions include a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), a metal complex of 10-hydroxybenzo [h] quinoline, and an oxadiazole derivative. , Distyrylbiphenyl derivative, silol derivative, 3-hydroxyflavon metal complex, 5-hydroxyflavon metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compound ( Japanese Patent Application Laid-Open No. 6-207169), phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-tert-butyl-9,10-N, N'-dicyanoanthraquinone diimine, n-type hydride amorphous silicon carbide , N-type zinc sulfide, n-type zinc selenium and the like.

As the material of the electron transport layer 7, only one kind may be used, or two or more kinds may be used in any combination and ratio.

There is no limitation on the method of forming the electron transport layer 7. Therefore, the electron transport layer 7 can be formed by a wet film forming method, a thin film deposition method, or other methods.

The film thickness of the electron transport layer 7 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

[8] Electron injection layer The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the light emitting layer 5. In order to efficiently perform electron injection, the material forming the electron injection layer 8 is preferably a metal having a low work function. As an example, alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like are used.

For example, lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II) (CsCO ₃ ) and the like can be mentioned (Applied Physics Letters, 1997, Vol. 70, p. 152). Japanese Patent Application Laid-Open No. 10-74586; IEEE Transactions on Electron Devices, 1997, Vol. 44, p. 1245; SID 04 Digest, p. 154, etc.).

The film thickness of the electron injection layer is usually preferably 0.1 nm or more and 5 nm or less.

Further, an organic electron transport compound typified by a nitrogen-containing heterocyclic compound such as basophenanthroline or a metal complex such as an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, and rubidium (). (Refer to JP-A No. 10-270171, JP-A-2002-100478, JP-A-2002-1000482, etc.), which is preferable because electron injection and transportability can be improved and excellent film quality can be achieved at the same time. .. In this case, the film thickness is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

As the material of the electron injection layer 8, only one kind may be used, or two or more kinds may be used in any combination and ratio.

There is no limitation on the method of forming the electron injection layer 8. Therefore, the electron injection layer 8 can be formed by a wet film forming method, a thin film deposition method, or other methods.

[9] Cathode The cathode 9 plays a role of injecting electrons into a layer (electron injection layer 8 or light emitting layer 5 or the like) on the light emitting layer 5 side.

As the material of the cathode 9, the material used for the anode 2 can be used, but in order to efficiently inject electrons, a metal having a low work function is preferable, for example, tin, magnesium, indium, and the like. Suitable metals such as calcium, aluminum and silver or alloys thereof are used. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.

As the material of the cathode 9, only one kind may be used, or two or more kinds may be used in any combination and ratio.

The film thickness of the cathode 9 is usually the same as the film thickness of the anode 2.

Further, for the purpose of protecting the cathode 9 made of a low work function metal, it is preferable to further laminate a metal layer having a high work function and stable to the atmosphere on the cathode 9 because the stability of the device is increased. Metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used for this purpose. In addition, these materials may be used only 1 type, and 2 or more types may be used together in arbitrary combinations and ratios.

[10] Other Layers The organic electroluminescent device of the present invention may have a different configuration as long as it does not deviate from the purpose. For example, an arbitrary layer may be provided between the anode 2 and the cathode 9 in addition to the layer described above, or any layer may be omitted as long as the performance is not impaired. ..

[11] Electron blocking layer An optional layer includes, for example, an electron blocking layer. The electron blocking layer is provided between the hole injection layer 3 or the hole transport layer 4 and the light emitting layer 5. By blocking the electrons moving from the light emitting layer 5 from reaching the hole injection layer 3 in the electron blocking layer, the recombination probability of holes and electrons in the light emitting layer 5 is increased and generated. It has a role of confining excitons in the light emitting layer 5 and a role of efficiently transporting holes injected from the hole injection layer 3 toward the light emitting layer 5. In particular, when a phosphorescent material is used as the light emitting material or a blue light emitting material is used, it is effective to provide an electron blocking layer.

The characteristics required for the electron blocking layer include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Further, when the light emitting layer 5 is manufactured by the wet film forming method, the electron blocking layer is also required to be compatible with the wet film forming method. Examples of the material used for such an electron blocking layer include the aromatic compound of the present invention, a copolymer of dioctylfluorene and triphenylamine represented by F8-TFB (International Publication No. 2004/084260), and the like. ..

As the material of the electron blocking layer, only one kind may be used, or two or more kinds may be used in any combination and ratio.

There is no limitation on the method of forming the electron blocking layer. Therefore, the electron blocking layer can be formed by a wet film forming method, a thin film deposition method, or other methods.

Further, in the layer configuration described above, components other than the substrate can be laminated in the reverse order. For example, in the layer configuration of FIG. 1, other components on the substrate 1 are the cathode 9, the electron injection layer 8, the electron transport layer 7, the hole blocking layer 6, the light emitting layer 5, the hole transport layer 4, and the positive. The hole injection layer 3 and the anode 2 may be provided in this order.

Further, the organic electroluminescent device of the present invention can be configured by laminating a component other than the substrate between two substrates having at least one of them being transparent.

It is also possible to have a structure in which a plurality of components (light emitting units) other than the substrate are stacked (a structure in which a plurality of light emitting units are stacked). In that case, (when the anode is ITO, the cathode is Al, these two layers) interfacial layer between the respective stages (between emission units) Alternatively, for example, a charge consisting of five vanadium oxide (V 2 _{O 5),} etc. When a carrier generation layer (CGL) is provided, the barrier between the stages is reduced, which is more preferable from the viewpoint of luminous efficiency and drive voltage.

Further, the organic electroluminescent device of the present invention may be configured as a single organic electroluminescent device, or may be applied to a configuration in which a plurality of organic electroluminescent devices are arranged in an array, and may be applied to an anode and a cathode. May be applied to configurations in which are arranged in an XY matrix.
Further, each of the above-mentioned layers may contain components other than those described as materials as long as the effects of the present invention are not significantly impaired.

The organic electroluminescent element of the present invention is used in a display device such as an organic EL display and a lighting device such as an organic EL lighting. By the organic electroluminescent device of the present invention, for example, by the method described in "Organic EL Display" (Ohm Co., Ltd., published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). Organic EL displays and organic EL lighting can be formed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination of the values of Examples.

In the present specification, Me means a methyl group, Et means an ethyl group, Ac means an acetyl group, Ph means a phenyl group, and dppf means 1,1'-bis (diphenylphos). Fino) Ferrocene, DMSO means dimethylsulfoxide, DME means 1,2-dimethoxyethane, DCM means dichloromethane, Tf means trifluoromethylsulfonyl group (CF ₃ SO _2- ) do.

<Example 1: Synthesis example of compound 1>
(Synthesis of Intermediate 1)

Dibenzofuran-4-boronic acid (10.4 g, 49.1 mmol), 1-bromo-3-iodobenzene (13.9 g, 49.1 mmol) with nitrogen bubbling toluene (100 mL), ethanol (61 mL), phosphorus An aqueous solution of tripotassium acid (2.0 mol / L, 61 mL) was added in order, and the mixture was heated to 55 ° C. Then, PdCl ₂ (PPh ₃ ) ₂ (0.34 g, 0.49 mmol) was added, and the mixture was stirred at 65 ° C. for 5 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 1 (yield 12.4 g, yield 78%).

(Synthesis of Intermediate 2)

Dehydrated DMSO (100 mL) was added to Intermediate 1 (12.4 g, 38.4 mmol), Bis (pinacolatodiborone) (14.6 g, 57.6 mmol), Potassium acetate (11.3 g, 115.2 mmol). It was heated to 50 ° C. PdCl ₂ (dppf) CH ₂ Cl ₂ (3.14 g, 3.84 mmol) was added, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, distilled water was added and suction filtration was performed. The filtrate was dissolved in dichloromethane, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 2 (yield 14.0 g, yield 99%).

(Synthesis of Intermediate 3)

Intermediate 2 (14.0 g, 37.8 mmol), 1-bromo-4-iodobenzene (10.7 g, 37.8 mmol) with nitrogen bubbling toluene (100 mL), ethanol (47 mL), tripotassium phosphate Aqueous solution (2.0 mol / L, 47 mL) was added in order and heated to 55 ° C. Then, PdCl ₂ (PPh ₃ ) ₂ (0.26 g, 0.37 mmol) was added, and the mixture was stirred at 65 ° C. for 6 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 3 (yield 9.90 g, yield 66%).

(Synthesis of Intermediate 4)

3-Terphenylboronic acid (10.1 g, 37.0 mmol), 1-bromo-4-iodobenzene (10.5 g, 37.0 mmol) with nitrogen bubbling toluene (100 mL), ethanol (46 mL), phosphorus An aqueous solution of tripotassium acid (2.0 mol / L, 46 mL) was added in order, and the mixture was heated to 55 ° C. Then, PdCl ₂ (PPh ₃ ) ₂ (0.26 g, 0.37 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 4 (yield 12.7 g, yield 89%).

(Synthesis of Intermediate 5)

Dehydrated DMSO (100 mL) was added to Intermediate 4 (10.4 g, 27.0 mmol), Bis (pinacolatodiboron) (10.3 g, 40.5 mmol) and Potassium acetate (7.95 g, 81.0 mmol). It was heated to 50 ° C. PdCl ₂ (dppf) CH ₂ Cl ₂ (1.10 g, 1.35 mmol) was added, and the mixture was stirred at 90 ° C. for 8 hours. After cooling to room temperature, distilled water was added and suction filtration was performed. The filtrate was dissolved in dichloromethane, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 5 (yield 10.7 g, yield 92%).

(Synthesis of Intermediate 6)

1-Bromo-2-dibenzofuranol (2.30 g, 8.74 mmol) and intermediate 5 (3.78 g, 8.74 mmol) were added with nitrogen bubbling dimethoxyethane (60 mL) and heated to 55 ° C. Aqueous potassium carbonate solution (2.0 mol / L, 15 mL) and Pd (PPh ₃ ) ₄ (0.10 g, 0.087 mmol) were added in this order, and the mixture was stirred at 90 ° C. for 6 hours. After cooling to room temperature, distilled water was added, and extraction was performed using ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 6 (yield 4.10 g, yield 96%).

(Synthesis of Intermediate 7)

Nitrogen bubbling dichloromethane (100 mL) and triethylamine (2.9 mL, 21.0 mmol) were added to Intermediate 6 (4.10 g, 8.39 mmol), and the mixture was cooled to −5 ° C. to −10 ° C. Trifluoromethanesulfonic anhydride (1.8 mL, 12.6 mmol) diluted with dichloromethane (20 mL) was added dropwise, and the mixture was stirred at −5 ° C. to −10 ° C. for 3 hours, and further at room temperature for 1 hour. Distilled water was added and extraction was performed using dichloromethane. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 7 (yield 4.90 g, yield 94%).

(Synthesis of Intermediate 8)

Dehydrated DMSO (100 mL) was added to Intermediate 7 (4.90 g, 7.89 mmol), Bis (pinacolatodiborone) (3.00 g, 11.8 mmol), Potassium acetate (2.32 g, 23.6 mmol). It was heated to 50 ° C. PdCl ₂ (dppf) CH ₂ Cl ₂ (0.64 g, 0.79 mmol) was added, and the mixture was stirred at 90 ° C. for 13 hours. After cooling to room temperature, distilled water was added and suction filtration was performed. The filtrate was dissolved in dichloromethane, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 8 (yield 0.94 g, yield 20%).

(Synthesis of Compound 1)

Intermediate 8 (0.94 g, 1.57 mmol), intermediate 3 (0.69 g, 1.73 mmol) with nitrogen bubbling toluene (6 mL), ethanol (2.0 mL), tripotassium phosphate aqueous solution (2) (0.0 mol / L, 2.0 mL) was added in order, and the mixture was heated to 55 ° C. Then, Pd (PPh ₃ ) ₄ (15 mg, 0.013 mmol) was added, and the mixture was stirred at 90 ° C. for 7 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Compound 1 (yield 0.98 g, yield 79%).

<Example 2: Synthesis of compound 2>
(Synthesis of Intermediate 9)

Toluene (100 mL) obtained by nitrogen bubbling of 3-terphenylboronic acid (8.02 g, 29.3 mmol) and 3-bromo-3'-iodo-1,1'-biphenyl (10.5 g, 29.3 mmol). , Ethanol (37 mL) and tripotassium phosphate aqueous solution (2.0 mol / L, 37 mL) were added in this order, and the mixture was heated to 60 ° C. Then, PdCl ₂ (PPh ₃ ) ₂ (0.20 g, 0.29 mmol) was added, and the mixture was stirred at 65 ° C. for 6 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 9 (yield 11.1 g, yield 82%).

(Synthesis of Intermediate 10)

Dehydrated DMSO (100 mL) was added to Intermediate 9 (5.00 g, 10.8 mmol), Bis (pinacolatodiborone) (4.14 g, 16.3 mmol), Potassium acetate (3.19 g, 32.5 mmol). It was heated to 50 ° C. PdCl ₂ (dppf) CH ₂ Cl ₂ (0.88 g, 1.08 mmol) was added, and the mixture was stirred at 90 ° C. for 5 hours. After cooling to room temperature, distilled water was added and suction filtration was performed. The filtrate was dissolved in dichloromethane, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 10 (yield 5.16 g, yield 94%).

(Synthesis of Intermediate 11)

Dimethoxyethane (40 mL) subjected to nitrogen bubbling was added to 1-bromo-2-dibenzofuranol (1.10 g, 4.18 mmol) and intermediate 10 (2.13 g, 4.18 mmol), and the mixture was heated to 55 ° C. Aqueous potassium carbonate solution (2.0 mol / L, 7.3 mL) and Pd (PPh ₃ ) ₄ (48 mg, 0.042 mmol) were added in this order, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, distilled water was added, and extraction was performed using ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 11 (yield 2.28 g, yield 97%).

(Synthesis of Intermediate 12)

Nitrogen bubbling dichloromethane (60 mL) and triethylamine (1.4 mL, 10.1 mmol) were added to Intermediate 11 (2.28 g, 4.04 mmol), and the mixture was cooled to −5 ° C. to −10 ° C. Trifluoromethanesulfonic anhydride (0.90 mL, 6.06 mmol) diluted with dichloromethane (20 mL) was added dropwise, and the mixture was stirred at −5 ° C. to −10 ° C. for 3 hours, and further at room temperature for 1 hour. Distilled water was added and extraction was performed using dichloromethane. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 12 (yield 2.63 g, yield 94%).

(Synthesis of Intermediate 13)

Dehydrated DMSO (35 mL) was added to Intermediate 12 (2.63 g, 3.77 mmol), Bis (pinacolatodiboron) (1.44 g, 5.66 mmol), Potassium acetate (1.11 g, 11.3 mmol). It was heated to 50 ° C. PdCl ₂ (dppf) CH ₂ Cl ₂ (0.15 g, 0.19 mmol) was added, and the mixture was stirred at 90 ° C. for 10 hours. After cooling to room temperature, distilled water was added and suction filtration was performed. The filtrate was dissolved in dichloromethane, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Intermediate 13 (yield 1.59 g, yield 63%).

(Synthesis of Compound 2)

Intermediate 13 (1.59 g, 2.36 mmol), intermediate 3 (1.04 g, 2.59 mmol) with nitrogen bubbling toluene (12 mL), ethanol (3.0 mL), tripotassium phosphate aqueous solution (2) (0.0 mol / L, 3.0 mL) was added in order, and the mixture was heated to 50 ° C. Then, Pd (PPh ₃ ) ₄ (27 mg, 0.024 mmol) was added, and the mixture was stirred at 90 ° C. for 10 hours. After cooling to room temperature, a saturated aqueous sodium chloride solution was added, and extraction was performed using toluene. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Compound 2 (yield 1.55 g, yield 76%).

<Evaluation of Compound 1 and Compound 2>
The glass transition temperatures (Tg) of Compound 1 and Compound 2 were evaluated by differential scanning calorimetry (DSC). The Tg of Compound 1 and Compound 2 was 125.4 ° C and 127.2 ° C, respectively.

1. 1. Substrate 2. Anode 3. Hole injection layer 4. Hole transport layer 5. Light emitting layer 6. Hole blocking layer 7. Electron transport layer 8. Electron injection layer 9. Cathode 10. Organic electroluminescent device

Claims (10)

An aromatic compound represented by the following general formula (1).

In the formula (1), R ¹ and R ² are independent of each other and are represented by the following general formula (2) or the following general formula (3), and R ³ is an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group. , Aryloxy group, alkoxycarbonyl group, acyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group, silyl group, syroxy group, cyano group, or aralkyl group, and a is an integer of 0 to 6. However, ^{at least one of R 1} and R ² is represented by the following general formula (2).

In the formula (2), the asterix (*) represents a bond with the formula (1), and Ar ¹ is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. n is an integer of 1 or more.

In the formula (3), the asterix (*) represents a bond with the formula (1), and Ar ² is a divalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ is a monovalent aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent, and m is an integer of 1 or more. An organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode.
An organic electroluminescent element, wherein the organic layer has a layer containing a material for an organic electroluminescent element, and the material for the organic electroluminescent element is the aromatic compound according to claim 1. The organic electroluminescent device according to claim 2, wherein the layer containing the material for the organic electroluminescent device is a light emitting layer. A display device having the organic electroluminescent device according to claim 2 or 3. A lighting device having the organic electroluminescent device according to claim 2 or 3. A composition containing the aromatic compound and solvent according to claim 1. The composition according to claim 6, further comprising a phosphorescent material and a host material. A thin film forming method comprising a step of forming a film of the composition according to claim 6 or 7 by a wet film forming method. A method for manufacturing an organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode.
A method for producing an organic electroluminescent device, which comprises a step of forming the organic layer by a wet film forming method using the composition according to claim 6 or 7. The method for manufacturing an organic electroluminescent device according to claim 9, wherein the organic layer is a light emitting layer.

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