TW201431861A - Compound having an acridan ring structure and organic electroluminescent device - Google Patents

Abstract

A compound having an acridan ring structure represented by the general formula (1), and an organic electroluminescent device having a pair of electrodes and at least one organic layer sandwiched there between. The compound is used as a material that constitutes the organic layer. The compound has excellent hole injection/transporting capability, electron blocking power, high degree of stability in the form of a thin film, excellent heat resistance, and is used as a material for the organic electroluminescent device that features high efficiency and large resistance.

Description

Compound having an acridine ring structure and organic electroluminescent element

The present invention relates to a compound of an organic electroluminescence device suitable for a self-luminous element of various display devices and the device, and more particularly to a compound having an acridine ring-filled structure and organic electroluminescence using the same element.

Since the organic electroluminescent element (hereinafter sometimes referred to as an organic EL element) is a self-luminous element, it is brighter than the liquid crystal element and has excellent visibility, and can be clearly displayed. Therefore, organic EL elements have been actively studied.

In 1987, CWTang et al. of Eastman Kodak Company developed a laminated structural element in which various functions were distributed to respective materials, and the organic electroluminescent element using an organic material was put into practical use. These are stacked with an aromatic electron compound capable of transporting electrons, that is, arsenic (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) and a hole capable of transporting holes, and the charges of both. Light is emitted into the phosphor layer to obtain a high luminance of 1000 cd/m ² or more at a voltage of 10 V or less (see, for example, Patent Document 1 and Patent Document 2).

Until now, there have been many improvements in the practical use of organic electroluminescent elements, and various functions have been further subdivided. It is known to sequentially provide an anode, a hole injection layer, a hole transport layer, a light-emitting layer, and an electron on a substrate. High-efficiency light-emitting elements of the transport layer, electron injection layer, and cathode With durability.

Others have attempted to utilize triplet excitons in order to improve luminous efficiency, and some have also explored the use of phosphorescent emitters.

Further, an element using luminescence of thermally activated delayed fluorescence (TADF) has been developed, and an external quantum efficiency of 5.3% has been achieved by using an element using a thermally activated delayed fluorescent material.

The light-emitting layer may be produced by doping a phosphor or a phosphorescent light-emitting compound in a charge transporting property generally called a host material. The choice of the organic material in the organic electroluminescent element can have a significant impact on the characteristics of the element such as efficiency or durability.

In the organic electroluminescence device, the charge injected from the two electrodes recombines in the light-emitting layer to obtain light emission, but how the two charges of the hole and the electron are transferred to the light-emitting layer with good efficiency is important, and the hole injection property is improved. The electron blocking property of the electrons injected from the cathode is blocked, the probability of recombination of the hole and the electrons is improved, and the high luminous efficiency can be obtained by the excitons generated in the light-emitting layer. Therefore, the role of the hole transporting material is important, and it is sought for a hole transporting material having high hole injection property, large mobility of the hole, high electron blocking property, and high durability to electrons.

Further, regarding the life of the element, heat resistance or amorphousness of the material is also important. A material having low heat resistance causes thermal decomposition and deterioration of the material even at a low temperature due to heat generated when the element is driven. A material having a low amorphous property may cause crystallization of the film even in a short period of time, resulting in deterioration of the element. Therefore, the material to be used is desired to have high heat resistance and good amorphous properties.

N,N'-diphenyl-N,N'-bis(α-naphthyl)benzidine (hereinafter abbreviated as NPD) and various aromatics are known as a hole transporting material used as an organic electroluminescence device. A group amine derivative (for example, refer to Patent Document 1 and Patent Document 2). NPD has a good hole transporting ability, but the glass transition point (Tg) which is an index of heat resistance is as low as 96 ° C, and the element characteristics are degraded due to crystallization under high temperature conditions. Further, among the aromatic amine derivatives described in Patent Document 1 or Patent Document 2, a compound having excellent mobility with a hole mobility of 10 ^-3 cm ² /Vs or more is known, but the electron blocking property is insufficient. Therefore, some electrons pass through the light-emitting layer, and improvement in luminous efficiency cannot be expected. In order to increase efficiency, materials with higher electron blocking properties, more stable film, and high heat resistance are being sought.

As a compound having improved properties such as heat resistance, hole injectability, and electron barrier property, an arylamine compound having a substituted acridan structure (for example, compounds A to C) represented by the following formula has been proposed (for example, reference) Patent Documents 3 to 5).

However, the components obtained by using these compounds in the hole injection layer or the hole transport layer have been improved, but have not been satisfactorily improved in heat resistance or luminous efficiency, and low driving voltage or current efficiency is not counted. Satisfactory, amorphous is also a problem. Therefore, seeking to improve the amorphousness and At the same time, the compound has a lower driving voltage or a higher luminous efficiency.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-048656

[Patent Document 2] Japanese Patent No. 3194657

Patent Document 3: WO2006/033563

Patent Document 4: WO2007/110228

Patent Document 5: WO2010/147319

An object of the present invention is to provide a material for an organic electroluminescence device having high efficiency and high durability, which is excellent in hole injection, high in transport performance, electron blocking ability, high in stability in a film state, and excellent in heat resistance. Characteristic organic compounds.

Another object of the present invention is to provide an organic electroluminescence device having high luminous efficiency and high durability using the compound.

The physical properties of the organic compound to be provided by the present invention include: (α) good hole injection characteristics, (β) hole mobility, (γ) electron blocking ability, (δ) film state stability, (ε) Excellent heat resistance.

Moreover, the physical characteristics of the organic electroluminescent element to be provided by the present invention include, for example, (α) high luminous efficiency and power efficiency, low (β) light-emission starting voltage, and low (γ) practical driving voltage.

In order to achieve the above object, the inventors of the present invention expect that the aromatic tertiary amine structure has high hole injection, transport capacity, and a predetermined acridine ring structure (benzothienoacene ring structure or benzofuran acridine). The full-ring structure has electron blocking property, and the heat resistance of the predetermined acridine ring-filled structure and the effect on the stability of the film, design and chemical synthesis of a compound having an acridine ring-ring structure, and using the compound to test various organic electricity In the light-emitting element, the characteristics of the element were evaluated, and as a result, the present invention was completed.

According to the present invention, there is provided a compound having an acridine ring-filled structure represented by the following formula (1).

In the formula, X represents an oxygen atom or a sulfur atom, and R ¹ to R ⁹ are a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 5~ a cycloalkyl group of 10, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensation a polycyclic aromatic group or an aryloxy group, and may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; R ¹⁰ and R ¹¹ are an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, and an aromatic group a heterocyclic group, a condensed polycyclic aromatic group or an aryloxy group, and may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; Ar ¹ , Ar ² , Ar ³ represent an aromatic group a hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, and Ar ² and Ar ³ may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; A represents an aromatic hydrocarbon, Aromatic heterocyclic or condensation The divalent aromatic group, or a single bond, A is a case where an aromatic hydrocarbon, an aromatic heterocyclic group or a divalent condensed polycyclic aromatic of, A and Ar ² may be via a single bond or a methylene group, an oxygen atom Or sulfur atoms are bonded to each other to form a ring.

Among the compounds of the present invention, the following aspects are preferred.

(I) R ¹ , R ² , R ³ and A are bonded at a position represented by the following formula (1-1) with respect to the benzene ring having an A bond.

In the formula, X, R ¹ to R ¹¹ , Ar ¹ to Ar ³ and A are as described in the above formula (1).

(II) A is a divalent group of an aromatic hydrocarbon or a condensed polycyclic aromatic.

(III) A is a divalent group of an aromatic hydrocarbon or a condensed polycyclic aromatic ring represented by the following formula (2).

Wherein r ¹² represents an integer of 0 to 4; R ¹² is a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 5 to 10 carbon atoms. , an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic complex ring group, and a condensed polycyclic aromatic group Or an aryloxy group, or a linking group, and in the case where a plurality of R ¹² are present, a plurality of R ¹² may form a ring with each other.

(IV) A is a divalent group of an aromatic hydrocarbon or a condensed polycyclic aromatic ring represented by the following formula (2 ' ).

In the formula, r ¹² and R ^{12 are} as defined in the above formula (2).

(V) As shown by the following formula (1-2), r ¹² =1 and R ¹² is a linking group, and the bonding position of R ¹² has been determined.

In the formula, X, R ¹ to R ¹¹ , Ar ¹ , Ar ³ and A are as defined in the above formulae (1) and (1-1); and Ar ⁴ represents the above formula (1) or (1-1) The divalent group in the group to which the Ar ² belongs is described, and Ar ³ and Ar ⁴ may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring.

(VI) A is a single bond.

Moreover, according to the present invention, there is provided an organic electroluminescence device comprising a pair of electrodes and at least one organic layer sandwiched between the pair of electrodes, wherein the compound having an acridine ring-ring structure is used as the organic The constituent materials of the layer.

In the organic electroluminescence device of the present invention, (VII) the organic layer-based hole transport layer, (VIII) the organic layer-based electron blocking layer, (IX) the organic layer-based hole injection layer, and (X) are preferable. The aforementioned organic layer is a light-emitting layer.

The compound having an acridine ring-ring structure of the present invention is a novel compound, and the predetermined acridine ring-filled structure (benzothienoacene ring structure or benzofuran acridine ring structure) has electron blocking property, and The established acridine ring structure has heat resistance and film stability. Therefore, the compound having an acridine ring-ring structure of the present invention is: (A) has excellent electron blocking ability; (B) has excellent amorphous property, and (C) has a stable film state.

Particularly, in the case of the (C) film state, the compound of the present invention has a high glass transition point (Tg) which is an index of heat resistance, and specifically has a Tg of 100 ° C or more, particularly 140 ° C or more. Therefore, the film formed using the compound of the present invention is not easily crystallized even under high temperature conditions.

The compound of the present invention can be used, for example, as a constituent material of a hole injection layer and/or a hole transport layer of an organic EL device. Compared with the conventional materials, the compound of the present invention has high injectability of the hole, (b) large mobility of the hole, (c) high electron blocking property, and (d) high stability to electrons. Therefore, the hole injection layer and/or the hole transport layer obtained by using the compound of the present invention as a constituent material can conceal excitons generated in the light-emitting layer, thereby improving the probability of recombination of holes and electrons, and obtaining It has high luminous efficiency and can impart a function of lowering the driving voltage and improving the durability of the organic EL element.

Further, the compound of the present invention can also be used as a constituent material of an electron blocking layer of an organic EL device. The compound of the present invention has (e) excellent electron blocking ability, (f) superior in hole transportability to conventional materials, and (g) high stability in film state, so that the compound of the present invention is used as The electron blocking layer made of the material has high luminous efficiency and has the following effects: the driving voltage is lowered, the current resistance is improved, and the maximum luminance of the organic EL element is improved.

Further, the compound of the present invention can also be used as a constituent material of the light-emitting layer of the organic EL device. The compound of the present invention, (h) is superior in hole transportability to a conventional material, and (i) has a wide energy gap, the material of the present invention is used as a host material of the light-emitting layer, and is called a dopant. A fluorescent illuminant or a phosphorescent illuminant is used as a luminescent layer to achieve a reduction in driving voltage and emission An organic EL element having improved light efficiency.

In the organic EL device of the present invention, the hole transporting material is used, the mobility of the hole is large, the electron blocking ability is excellent, and the amorphous state is excellent, and the film state is stable. The ring structure compound can achieve high efficiency and high durability.

In the above, the compound having an acridine ring-ring structure of the present invention is useful as a constituent material of a hole injection layer, a hole transport layer, an electron blocking layer or a light-emitting layer of an organic EL device, and has excellent electron blocking ability and excellent properties. The electron blocking ability is good, the amorphous state is good, the film state is stable, and the heat resistance is excellent. The organic EL device of the present invention has high luminous efficiency and power efficiency, whereby the practical driving voltage of the device can be reduced. It can reduce the initial voltage of light emission and improve durability.

1‧‧‧ glass substrate

2‧‧‧Transparent anode

3‧‧‧ hole injection layer

4‧‧‧ hole transport layer

5‧‧‧Lighting layer

6‧‧‧Electronic transport layer

7‧‧‧Electronic injection layer

8‧‧‧ cathode

Figure 1 shows a ¹ H-NMR chart of the compound of Example 1 (Compound 2).

Figure 2 shows a ¹ H-NMR chart of the compound of Example 2 (Compound 20).

Figure 3 shows a ¹ H-NMR chart of the compound of Example 3 (Compound 27).

Figure 4 shows a ¹ H-NMR chart of the compound of Example 4 (Compound 4).

Figure 5 shows a ¹ H-NMR chart of the compound of Example 5 (Compound 25).

Figure 6 shows a ¹ H-NMR chart of the compound of Example 6 (Compound 41).

Figure 7 shows a ¹ H-NMR chart of the compound of Example 7 (Compound 42).

Figure 8 shows a ¹ H-NMR chart of the compound of Example 8 (Compound 23).

Fig. 9 shows the EL element configurations of Examples 11 to 18 and Comparative Example 1.

The compound of the present invention is represented by the following formula (1) and has a predetermined acridine ring-ring structure and an aromatic tertiary amine structure.

Among the compounds of the present invention represented by the above formula (1), R ¹ , R ² , R ³ and A in the A-bonded benzene ring are preferably bonded at positions represented by the following formula (1-1). Compound.

<X>

X represents an oxygen atom or a sulfur atom. When X is a sulfur atom, the compound of the present invention has a benzothienoacene ring structure. Further, when X is an oxygen atom, the compound of the present invention has a benzofuranacidine acyclic structure.

<R ¹ ~R ⁹ >

R ¹ to R ⁹ may be the same or different and each represents a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 5 to 10 carbon atoms. , an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group Or aryloxy. These groups may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms are as follows.

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1 -adamantyl, 2-adamantyl, B Alkenyl, allyl, isopropenyl, 2-butenyl and the like.

As understood from the above examples, the alkyl group having 1 to 6 carbon atoms or the alkenyl group having 2 to 6 carbon atoms represented by R ¹ to R ⁹ may be linear or branched.

The alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms represented by R ¹ to R ⁹ may have a substituent. The following examples are mentioned as a substituent.

Helium atom; cyano; nitro; halogen atom, such as fluorine atom, chlorine atom, bromine atom, iodine atom; linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy group, ethoxy group Alkenyl, propoxy; alkenyl, such as allyl; aryloxy, such as phenoxy, tolyloxy; arylalkoxy, such as benzyloxy, phenethyloxy; aromatic hydrocarbyl or condensed polycyclic Aromatic group, for example, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthryl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl An aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, oxazolyl, benzo Azolyl, benzothiazolyl, quin A phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a porphyrin group; these substituents may also have a more substituent. Further, the substituent may be the same as the above substituent. The substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the alkoxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by R ¹ to R ⁹ include the following examples.

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptane Oxyl, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy and the like.

As understood from the above examples, the alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ may be linear or branched.

The alkoxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by R ¹ to R ⁹ may have a substituent. The substituent may be an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. For the same example. Further, the substituents may have more substituents. Further, the substituent may be an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The substituents are the same. The above-exemplified substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by R ¹ to R ⁹ include the following examples.

Phenyl, biphenyl, tert-triphenyl, naphthyl, anthracenyl, phenanthryl, anthryl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl, pyridyl, furan Base, pyrrolyl, thienyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzene Azolyl, benzothiazolyl, quin A phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a porphyrin group, or the like.

The aromatic heterocyclic group represented by R ¹ to R ⁹ is preferably a sulfur-containing aromatic heterocyclic group such as a thienyl group, a benzothienyl group, a benzothiazolyl group or a dibenzothiophenyl group.

The aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by R ¹ to R ⁹ may have a substituent. The following examples are mentioned as a substituent.

Helium atom; trifluoromethyl; cyano; nitro; halogen atom, such as fluorine atom, chlorine atom, bromine atom, iodine atom; linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl group , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl; linear chain of 1 to 6 carbon atoms Or branched alkoxy groups, such as methoxy, ethoxy, propoxy; alkenyl, such as allyl; aralkyl, such as benzyl, naphthylmethyl, phenethyl; aryloxy, For example, phenoxy, tolyloxy; arylalkoxy, such as benzyloxy, phenethyloxy; aromatic hydrocarbon group or condensed polycyclic aromatic group, for example: phenyl, biphenyl, terphenyl, Naphthyl, anthracenyl, phenanthryl, anthryl, fluorenyl, fluorenyl, fluorenyl, allyldienyl, hydrazine; aromatic heterocyclic group, such as pyridyl, thienyl, furyl, Pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Azolyl, benzothiazolyl, quin a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; an anthracenyl group such as an acetamino group a benzylamino group; a dialkylamino group, such as a dimethylamino group, a diethylamino group; a disubstituted amino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group, such as a diphenylamino group or a dinaphthylamino group; a diarylalkylamino group, such as a dibenzylamino group, a diphenylethylamino group; a disubstituted amino group substituted with an aromatic heterocyclic group, such as a dipyridylamino group, a dithienylamino group; a dienylamino group, For example, a diallylamine group; a disubstituted amine group substituted with a substituent selected from an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, an aromatic heterocyclic group or an alkenyl group; the substituents It may also have a substituent. The more preferable substituent is the same as the above-mentioned substituent which is possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ . Further, the substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the aryloxy group represented by R ¹ to R ⁹ include the following examples.

Phenoxy, biphenyloxy, terphenyltrioxy, naphthyloxy, anthracenyloxy, phenanthryloxy, anthracenyloxy, decyloxy, decyloxy, decyloxy and the like.

The aryloxy group represented by R ¹ to R ⁹ may have a substituent. The substituent may be the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. These substituents may also have more substituents. The more preferable substituent is the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. The substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

<R ¹⁰ , R ¹¹ >

R ¹⁰ and R ¹¹ may be the same or different and each represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 1 to 6 carbon atoms. An alkoxy group, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, a condensed polycyclic aromatic group or an aryloxy group. These groups may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁰ and R ¹¹ , the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms include carbons represented by R ¹ to R ⁹ . The alkyl group having 1 to 6 atomic atoms, the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms is the same.

As understood from the exemplified group, the alkyl group having 1 to 6 carbon atoms or the alkenyl group having 2 to 6 carbon atoms represented by R ¹⁰ and R ¹¹ may be linear or branched.

The alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms represented by R ¹⁰ and R ¹¹ may have a substituent. The substituent may be an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. For the same example. These substituents may also have more substituents. Further, examples of the substituent include an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The substituents are the same. The substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the alkoxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by R ¹⁰ and R ¹¹ include an alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ . The same or an example is the cycloalkyloxy group having 5 to 10 carbon atoms.

As understood from the exemplified group, the alkoxy group having 1 to 6 carbon atoms may be linear or branched.

The alkoxy group having 1 to 6 carbon atoms or the cycloalkoxy group having 5 to 10 carbon atoms represented by R ¹⁰ and R ¹¹ may have a substituent. The substituent may be a substituent which may be possessed by an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. For the same example. Further, the substituents may have more substituents. Further, examples of the substituent include an alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The substituents are the same. The above-exemplified substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by R ¹⁰ and R ¹¹ include an aromatic hydrocarbon group represented by R ¹ to R ⁹ , an aromatic heterocyclic group or a condensed polycyclic aromatic group. The base is the same example.

The aromatic heterocyclic group represented by R ¹⁰ and R ¹¹ is preferably a sulfur-containing aromatic heterocyclic group such as a thienyl group, a benzothienyl group, a benzothiazolyl group or a dibenzothiophenyl group.

The aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by R ¹⁰ and R ¹¹ may have a substituent. The substituent may be the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. These substituents may also have more substituents. The more preferable substituent is the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. The substituents may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

Examples of the aryloxy group represented by R ¹⁰ and R ¹¹ include the same examples as the aryloxy group represented by R ¹ to R ⁹ .

The aryloxy group represented by R ¹⁰ and R ¹¹ may have a substituent. The substituent may be the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. These substituents may also have more substituents. The more preferable substituent is the same as the substituent which may be possessed by the aromatic hydrocarbon group represented by R ¹ to R ⁹ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. The substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

<Ar ¹ , Ar ² , Ar ³ >

Ar ¹ , Ar ² and Ar ³ may be the same or different and each represent an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group. The groups of Ar ¹ , Ar ² and Ar ³ may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent, for example, Ar ² and Ar ³ may also be via a single bond. Or it may have a methylene group, an oxygen atom or a sulfur atom of a substituent and bond to each other to form a ring.

Examples of the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by Ar ¹ , Ar ² and Ar ³ include an aromatic hydrocarbon group represented by R ¹ to R ⁹ , an aromatic heterocyclic group or a condensation. The cyclic aromatic group is the same.

The aromatic heterocyclic group represented by Ar ¹ , Ar ² or Ar ³ is preferably a sulfur-containing aromatic heterocyclic group such as a thienyl group, a benzothienyl group, a benzothiazolyl group or a dibenzothiophenyl group; or a furyl group; Benzofuranyl, benzo An oxygen-containing aromatic heterocyclic ring such as an azole group or a dibenzofuranyl group; preferably.

The aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by Ar ¹ , Ar ² or Ar ³ may have a substituent. The following examples are mentioned as a substituent.

Helium atom; cyano; nitro; halogen atom, such as fluorine atom, chlorine atom, bromine atom, iodine atom; linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, positive Propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl; linear or branched alkane having 1 to 6 carbon atoms Oxyl group, such as methoxy, ethoxy, propoxy; alkenyl, such as allyl; aryloxy, such as phenoxy, tolyloxy; arylalkoxy, such as benzyloxy, phenyl Oxyl; aromatic hydrocarbon group or condensed polycyclic aromatic group, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, propylene An alkene group, a triphenylene group or the like; an aromatic heterocyclic group such as a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, Mercapto, carbazolyl, benzo Azolyl, benzothiazolyl, quin a phenyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a porphyrin group, etc.; an arylvinyl group such as a styryl group, a naphthylvinyl group or the like; a fluorenyl group such as B Anthracenyl, benzamyl, and the like; in addition, the substituents may have more substituents. The more preferable substituent is the same as the substituent which is possessed by an aromatic hydrocarbon group represented by Ar ¹ , Ar ² or Ar ³ .

The substituents or the substituents and Ar ¹ , Ar ² , and Ar ³ may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

As Ar ¹ , an aromatic hydrocarbon group, a sulfur-containing aromatic heterocyclic group or a condensed polycyclic aromatic group is preferable, and a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a thienyl group, a benzothiophene group are particularly preferable. The phenyl group, the diphenylthiophene group, the phenyl group, the biphenyl group, the fluorenyl group, the benzothienyl group, and the dibenzothiophene group are most preferred.

Ar ² and Ar ^{3 are} preferably an aromatic hydrocarbon group, an oxygen-containing aromatic heterocyclic group, a sulfur-containing aromatic heterocyclic group or a condensed polycyclic aromatic group, and particularly preferably a phenyl group, a biphenyl group or a triphenyl group. , naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, most preferably Phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl.

<A>

A represents a divalent group or a single bond of an aromatic hydrocarbon, an aromatic heterocyclic ring or a condensed polycyclic aromatic group. Examples of the aromatic hydrocarbon, the aromatic heterocyclic ring and the condensed polycyclic aromatic compound include the following examples.

Benzene, biphenyl, terphenyl, tetracene, styrene, naphthalene, anthracene, acenaphthalene, anthracene, phenanthrene, anthracene, anthracene, pyridine, pyrimidine, three , furan, pyrrole, thiophene, quinoline, isoquinoline, benzofuran, benzothiophene, porphyrin, carbazole, porphyrin, benzo Azole, benzothiazole, quin Porphyrin, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene, Pyridine, phenanthroline, acridine, and the like.

The divalent group represented by A is produced by removing two hydrogen atoms from the above aromatic hydrocarbon, aromatic heterocyclic ring or condensed polycyclic aromatic.

As the aromatic heterocyclic ring, it is preferably a sulfur-containing aromatic heterocyclic ring such as thiophene, benzothiophene, benzothiazole or dibenzothiophene; or furan, benzofuran or benzo An oxygen-containing aromatic heterocyclic ring such as an azole or a dibenzofuran is preferred.

The aromatic hydrocarbon, the aromatic heterocyclic ring or the condensed polycyclic aromatic group may have a substituent. The substituent may be the same as the substituent which may be possessed by an aromatic hydrocarbon represented by Ar ¹ , Ar ² or Ar ³ , an aromatic heterocyclic ring or a condensed polycyclic aromatic group.

These substituents may also have more substituents. The more preferable substituents are the same as those which may be possessed by the aromatic hydrocarbon group represented by Ar ¹ , Ar ² or Ar ³ , the aromatic heterocyclic group or the condensed polycyclic aromatic group. Further, the substituents may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent to form a ring.

As A, a divalent group of an aromatic hydrocarbon or a divalent group or a single bond of a condensed polycyclic aromatic is preferable, and a divalent group or a single bond derived from benzene is particularly preferable.

When A is a single bond, the compound having an acridine ring-ring structure of the present invention is specifically represented by the following formula (1-3); It is desirable that the bonding positions of R ¹ to R ³ and Ar ³ Ar ² N- have been determined as shown by the following formula (1-4).

a divalent group derived from benzene, specifically represented by the following formula (2); , ideally represented by the following formula (2 ' );

r ¹² represents the number of radicals R ^{12 which} will be described later in detail, and is an integer of 0-4. r ¹² is 0, which means that the benzene ring in formula (2) or formula (2 ' ) is not substituted by R ¹² (hydrogen is present at the position of R ¹² ).

R ¹² represents a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and carbon. An alkoxy group having 1 to 6 atomic atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, a condensed polycyclic aromatic group or an aryloxy group or a linking group. When a large number of R ¹² is present (when r ¹² is 2 or more), most of R ¹² may be bonded to each other via a single bond or a methylene group having an substituent, an oxygen atom or a sulfur atom to form a ring.

The alkyl group having 1 to 6 carbon atoms represented by R ¹² , the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms may be exemplified by the number of carbon atoms represented by R ¹ to R ⁹ . The alkyl group of ~6, the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms is the same. Examples of the substituent which may be possessed by the group include an alkyl group having 1 to 6 carbon atoms represented by the above R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or a carbon atom number 2 The examples of the alkenyl group of ~6 are the same. Further, an ideal aspect may be exemplified with respect to the alkyl group having 1 to 6 carbon atoms represented by the above R ¹ to R ⁹ , a cycloalkyl group having 5 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The same is true.

Examples of the alkoxy group having 1 to 6 carbon atoms or the cycloalkoxy group having 5 to 10 carbon atoms represented by R ¹² include an alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ⁹ or carbon. The cycloalkoxy group having an atomic number of 5 to 10 is the same. Examples of the substituent which may be possessed by the above-mentioned groups include those having an alkoxy group having 1 to 6 carbon atoms or a cycloalkyloxy group having 5 to 10 carbon atoms represented by the above R ¹ to R ⁹ . The same example. Further, the preferred embodiment is also the same as those exemplified for the alkoxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by the above R ¹ to R ⁹ .

Examples of the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by R ¹² include an aromatic hydrocarbon group represented by R ¹ to R ⁹ , an aromatic heterocyclic group or a condensed polycyclic aromatic group. The example is the same example. Examples of the substituent which may be possessed by the above-mentioned groups are the same as those exemplified for the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by the above R ¹ to R ⁹ . Further, the ideal aspect is also the same as those exemplified for the aromatic hydrocarbon group, the aromatic heterocyclic group or the condensed polycyclic aromatic group represented by the above R ¹ to R ⁹ .

The aryloxy group represented by R ¹² may be the same as those exemplified as the aryloxy group represented by R ¹ to R ⁹ . The substituent which may be possessed as such a group may be the same as those exemplified for the aryloxy group represented by the above R ¹ to R ⁹ . Further, the ideal aspect is also the same as that exemplified for the aryloxy group represented by the above R ¹ to R ⁹ .

When R ¹² is a linking group, a benzene ring having an R ¹² bond and Ar ² may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom which may have a substituent, and is preferably formed as follows. As shown in the formula (1-2), a benzene ring having an R ¹² bond and Ar ⁴ are bonded to each other via a single bond to form a ring.

Ar ⁴ represents a divalent group of Ar ² . That is, as Ar ⁴ , a divalent group derived from the same group as the one described for Ar ^{2 is} exemplified. The substituent which may be possessed as the group constituting Ar ⁴ may be the same as those exemplified for the above Ar ² . Further, the desired aromatic heterocyclic group may be the same as those exemplified for the above Ar ² . Ar ⁴ and Ar ³ may be bonded to each other via a single bond or a methylene group having an substituent, an oxygen atom or a sulfur atom to form a ring.

<Manufacturing method>

The compound having an acridine ring-filled structure of the present invention is a novel compound which can be synthesized, for example, by the following method.

Among the compounds of the present invention, the synthesis method of a compound having a benzothienoacene ring structure (X is a sulfur atom) is specifically described.

First, methyl 2-(dibenzothiophen-2-yl)aminobenzoate was synthesized by the reaction of methyl 2-aminobenzoate with 2-bromodibenzothiophene.

Next, the obtained methyl 2-(dibenzothiophen-2-yl)aminobenzoate is reacted with methylmagnesium chloride to synthesize 2-{2-(dibenzothiophen-2-yl)amino)phenyl }propan-2-ol, followed by cyclization to synthesize 13,13-dimethyl-8,13-dihydrobenzothieno[3,2-a]acridine.

The condensation reaction of the 13,13-dimethyl-8,13-dihydrobenzothieno[3,2-a]acridine with an aryl halide can be carried out, for example, by performing a Buchwald-Hartwig reaction to synthesize an 8-position An aryl substituted benzothienoacridinium derivative.

Then, bromination of N-bromosuccinimide or the like is carried out to synthesize a brominated benzothienoacridinium derivative at position 11. Further, if the reagent or condition for bromination is changed at this time, a bromine substituent having a different substitution position can be obtained.

Furthermore, by using this bromine substituent with various boric acids or borate esters {refer to J. Org. Chem. , 60, 7508 (1995)} A cross-coupling reaction, such as Suzuki coupling {see Synth. Commun., 11, 513 (1981)}, can be used to synthesize a compound having a benzothienoacridane ring structure of the present invention.

On the other hand, among the compounds of the present invention, a compound having a benzofuranacidine acyclic structure (X is an oxygen atom), which can synthesize the above compound of the present invention having a benzothienopyridine ring structure In the reaction of methyl 2-aminobenzoate with 2-bromodibenzothiophene in the method, 2-bromodibenzofuran is used instead of 2-bromodibenzothiophene, followed by the same synthesis reaction.

Further, the compound having an acridine ring-ring structure of the present invention can be synthesized by the following method. That is, the benzothienopyridine ring structure of the present invention can be subjected to Buchwald-Hartwig reaction by reacting a bromine substituent of the above 8-position phenylthiophene acridinium derivative substituted with an aryl group with various diarylamines. Equal cross-coupling reactions to synthesize.

Similarly, the compound of the present invention having a benzofuranacidine acyclic structure can be subjected to Buchwald by using the bromine substituent of the above 8-position aryl-substituted benzofuran-acridinium derivative with various diarylamines. A cross-coupling reaction such as a Hartwig reaction to synthesize.

The purification of the obtained compound can be carried out by column chromatography, adsorption purification using tannin extract, activated carbon, activated clay or the like; recrystallization or crystallization using a solvent; and the like. Identification of the obtained compound was carried out by NMR analysis.

As the physical property value of the obtained compound, the glass transition point (Tg) and the work function were measured. The glass transition point (Tg) is an indicator of the stability of the film state. The work function is the indicator of the transportability of the hole.

The glass transition point (Tg) is obtained by, for example, using a powder with a high-sensitivity differential scanning calorimeter (manufactured by Bruker‧AXS, DSC3100SA).

For the work function, a film of 100 nm was formed on an ITO substrate, and it was measured using a free potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd., PYS-202 type).

Ideally among the compounds having the acridine ring-ring structure of the present invention represented by the above formula (1) Specific examples of the compound are as follows. Also, Compound 1 is missing.

<Organic EL element>

The organic EL device having the organic layer formed using the compound of the acridine ring-ring structure of the present invention has, for example, a layer structure as shown in FIG.

that is. The transparent anode 2, the hole injection layer 3, the hole transport layer 4, the light-emitting layer 5, the electron transport layer 6, and the electron injection layer 7 are provided on the glass substrate 1 (a transparent resin substrate or the like as long as it is a transparent substrate). Cathode 8.

Of course, the organic EL device to which the compound having an acridine ring-ring structure of the present invention is applied is not limited to the above layer structure. For example, an electron blocking layer (not shown) may be provided between the hole transport layer 4 and the light-emitting layer 5. Further, several layers of the organic layer may be omitted in the multilayer structure. That is, the hole injection layer 3 between the transparent anode 2 and the hole transport layer 4, or the electron injection layer 7 between the electron transport layer 6 and the cathode 8 may be omitted, and the anode 2 and the hole may be formed on the substrate 1. A simple configuration of the transport layer 4, the light-emitting layer 5, the electron transport layer 6, and the cathode 8.

The compound having an acridine ring-ring structure of the present invention is preferably used as an organic layer provided between the transparent anode 2 and the cathode 8 (for example, a hole injection layer 3, a hole transport layer 4, and an electron blocking layer not shown). Or a material for forming the light-emitting layer 5).

In the above organic EL device, the transparent anode 2 may be formed of an electrode material known per se, for example, by depositing an electrode material having a large work function such as ITO, such as gold, on the substrate 1 (transparent substrate such as a glass substrate). form.

Further, the hole injection layer 3 provided on the transparent anode 2 can be formed using the above-described compound having an acridine ring-ring structure of the present invention, or can be formed using a conventionally known material such as the following material.

a polyporphyrin compound represented by the cerium cyanine; a triphenylamine derivative of the ray type; an aromatic amine having a structure obtained by linking a plurality of triphenylamine skeletons with a single bond or a divalent group containing no hetero atom ( For example, a tetramer of triphenylamine, etc.; an acceptor heterocyclic compound such as hexacyanoazide heterotriphenyl; a coated polymer material such as poly(3,4-ethylenedioxythiophene) Hereinafter, it is abbreviated as PEDOT), poly(styrenesulfonate) (hereinafter referred to as PSS), and a layer (film) formed of the above material may be formed by a known method such as a spin coating method or a spray coating method in addition to the vapor deposition method. The various layers described below are also similar, and can be formed by vapor deposition, spin coating, spray coating, or the like.

The hole transport layer 4 provided on the hole injection layer 3 may be formed using the compound having the acridine ring-ring structure of the present invention, or may be formed using a conventionally known hole transport material. As such a conventionally known hole transporting material, the representative is as follows.

a benzidine derivative such as N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (hereinafter abbreviated as TPD); N,N'-diphenyl-N,N'-di ( Α-naphthyl)benzidine (hereinafter abbreviated as NPD); N,N,N',N'-tetraphenylbenzidine; amine derivative, for example: 1,1-bis[4-(di-4-A) Anilino)phenyl]cyclohexane (hereinafter abbreviated as TAPC); various triphenylamine trimers and tetramers; and the above-mentioned coated polymer materials for use as a hole injection layer; The compound which is the material for the hole transporting material may be separately formed into a film, or two or more types may be mixed and formed into a film, or a plurality of layers or a plurality of the above compounds may be used to form a plurality of layers and the layers may be laminated. The resulting multilayer film is used as the hole transport layer 4.

Further, it is also possible to form a layer which also serves as the hole injection layer 3 and the hole transport layer 4, and such a hole injection/transport layer can be formed by coating using a polymer material such as PEDOT.

Further, in the hole transport layer 4 (the same applies to the hole injection layer 3), P-type doped bromoxyaniline hexachloropyrene or the like may be further used for the material generally used for the layer. Further, the hole transport layer 4 may be formed using a polymer compound having a basic skeleton of TPD (the same applies to the hole injection layer 3).

Further, an electron blocking layer (which may be disposed between the light-emitting layer 5 and the hole transport layer 4), which is not shown, may be formed using a compound having an acridine ring-ring structure of the present invention having an electron blocking effect, but may also be used. It is formed using a known electron blocking compound such as a carbazole derivative or a compound having a phenylhydrazine group and a triarylamine structure. Specific examples of the carbazole derivative and the compound having a triarylamine structure are as follows.

(carbazole derivative)

4,4',4"-tris(N-carbazolyl)triphenylamine (hereinafter abbreviated as TCTA); 9,9-bis[4-(carbazol-9-yl)phenyl]anthracene; (carbazol-9-yl)benzene (hereinafter abbreviated as mCP); 2,2-bis(4-oxazol-9-ylphenyl)adamantane (hereinafter referred to as Ad-Cz);

(a compound having a triphenylsulfonyl group and a triarylamine structure)

9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylindenyl)phenyl]-9H-indole; an electron blocking layer capable of having the acridine ring structure of the present invention The compound is formed either alone or in combination of two or more kinds of the above-mentioned known materials. Further, a multilayer film obtained by laminating a plurality of layers of one or more of these materials and laminating such a layer can be used as an electron blocking layer.

The light-emitting layer 5 of the organic EL device of the present invention can be formed, for example, by the following light-emitting material.

a metal complex of a quinoline phenol derivative such as Alq ₃ ; various metal complexes such as zinc or beryllium, aluminum; an anthracene derivative; a bisstyrylbenzene derivative; an anthracene derivative; An azole derivative; a polyparaphenylenevinylene derivative.

Further, the light-emitting layer 5 may be composed of a host material and a dopant material.

As the host material, in addition to the above-mentioned luminescent material, a compound having an acridine ring-ring structure of the present invention can be used, and in addition to the above luminescent material, a thiazole derivative, a benzimidazole derivative, or a polydialkyl anthracene derivative can also be used. Wait.

As the dopant material, quinacridone, coumarin, erythritol, hydrazine and derivatives thereof; benzopyran derivatives, rhodamine derivatives; amino styryl groups can be used. Derivatives, etc.

The light-emitting layer 5 may be a single layer structure using one or two or more kinds of light-emitting materials, or may have a multilayer structure in which a plurality of layers are laminated.

Further, the light-emitting layer 5 may be formed using a phosphorescent material as a light-emitting material.

As the phosphorescent material, a phosphorescent emitter of a metal complex such as ruthenium or platinum can be used. For example, a green phosphorescent emitter such as Ir(ppy) ₃ , a blue phosphorescent emitter such as FIrpic or FIr6, or a red phosphorescent emitter such as Btp ₂ Ir(acac), which can be doped into a hole injection. It is used as a host material for transportability or as a host material for electron transport.

As a host material for hole injection and transportability, a compound having an acridine ring-ring structure of the present invention or 4,4'-di(N-carbazolyl)biphenyl (hereinafter referred to as CBP) or TCTA or mCP can be used. Equivalent oxazole derivatives, etc.

As a host material for electron transportability, p-bis(triphenylsulfonyl)benzene (hereinafter abbreviated as UGH2) or 2,2',2"-(1,3,5-phenylene)-parallel (1- Phenyl-1H-benzimidazole (hereinafter abbreviated as TPBI), etc. By using these, a high-performance organic EL device can be produced.

Further, in order to avoid concentration extinction, it is preferable that the phosphorescent luminescent material is doped with respect to the host material in a range of from 1 to 30% by weight based on the total amount of the light-emitting layer.

Further, a material which emits delayed fluorescence such as a CDCB derivative such as PIC-TRZ, CC2TA, PXZ-TRZ or 4CzIPN may be used as the luminescent material (refer to Appl. Phys. Let., 98, 083302 (2011)}.

A hole blocking layer (not shown in Fig. 9) which can be provided between the light-emitting layer 5 and the electron-transporting layer 6 can be formed using a compound having a well-known hole blocking action itself. As a known compound having such a hole blocking action, for example, the following.

A phenanthroline derivative, such as Bathocuproin (hereinafter referred to as BCP); a metal complex of a quinolinol derivative such as bis(2-methyl-8-quinolinic acid)-4-phenylphenol Aluminum (III) (aluminum (III) bis(2-methyl-8-quinolinate)-4-phenylphenolate, hereinafter referred to as BAlq); various rare earth complexes; triazole derivatives III derivative The oxadiazole derivative; these materials may be used in the formation of the electron transport layer 6 described below, or may be used together for the hole barrier layer and the electron transport layer 6.

Such a hole blocking layer may be a single layer or a multilayered laminated structure, and each layer may be formed by one or more kinds of the above-described compounds having a hole blocking action.

As the electron transport layer 6, an electron transporting compound known per se can be used, for example, a metal complex of a quinoline phenol derivative such as Alq ₃ or BAlq; a complex of various metals such as zinc or bismuth or aluminum; Azole derivative; three derivative; Diazole derivative; thiadiazole derivative; carbodiimide derivative; quin A morphological derivative; a phenanthroline derivative; a silole derivative or the like.

The electron transport layer 6 may be formed into a single layer or a multilayer laminate structure, and each layer may be formed by using one or more of the above electron transporting compounds.

Further, the electron injecting layer 7 may be used by itself. For example, an alkali metal salt such as lithium fluoride or cesium fluoride; an alkaline earth metal salt such as magnesium fluoride; a metal oxide such as alumina; or the like may be used.

For the cathode 8 of the organic EL element, an electrode material having a low work function such as aluminum or an alloy having a lower work function of a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy can be used as the electrode material.

Organic EL element forming at least one organic layer (for example, hole injection layer 3, hole transport layer 4, electron blocking layer or light-emitting layer 5) using the compound having an acridine ring-ring structure of the present invention, luminous efficiency and power efficiency High, practical driving voltage is low, and the light-emitting starting voltage is also low, which has excellent durability.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

<Example 1 (Synthesis of Compound 2)>

13,13-Dimethyl-8-phenyl-11-(9-phenyl-9H-indazol-3-yl)-8,13-dihydrobenzothieno[3,2-a]acridine Synthesis

The following compound was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Second, join

It was heated and stirred at 115 ° C for 3 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by liquid separation.

The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material.

The obtained crude product was purified by column chromatography (support: silica gel, eluent: toluene/n-hexane) to obtain a yellow powder of methyl 2-{(dibenzothiophen-2-yl)amino}benzoate. 5.1 g (yield 40%).

will

The reaction vessel was replaced with nitrogen, and 18 ml of a solution of methylmagnesium chloride in THF (3 mol/L) was added dropwise. After stirring at room temperature for 1 hour, 50 ml of a 20% aqueous ammonium chloride solution was added, and the organic layer was collected by extraction with toluene. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2-[2-{(dibenzothiophen-2-yl)amino}phenyl]propan-2-ol as pale yellow oil 5.0 g (Yield 100%).

2-[2-{(dibenzothiophen-2-yl)amino}phenyl]propan-2-ol 5.0g

Phosphoric acid 10ml

It was added to a reaction vessel substituted with nitrogen, and stirred at room temperature for 1 hour. After adding 50 ml of toluene and 50 ml of water and stirring, the precipitate was collected by filtration to obtain pale yellow powder of 13,13-dimethyl-8,13-dihydrobenzothieno[3,2-a]acridine. g (yield 49%).

will

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Join

It was heated and stirred at 115 ° C for 1 hour. After cooling to room temperature and adding 200 ml of water, the organic layer was collected by extraction with toluene. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 13,13-dimethyl-8-phenyl-8,13-dihydrobenzothiophene [3] , 2-a] acridine white powder 17.9 g (yield 72%).

will

It was placed in a reaction vessel substituted with nitrogen, and stirred at 15 ° C for 4 hours while cooling. After being added to water, the precipitate was collected by filtration. After adding methanol to the precipitate and stirring, 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzothieno[3,2-a]acridine was obtained by filtration. White powder 21.0 g (yield 98%).

will

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.8 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 72 ° C for 3 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by liquid separation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 13,13-dimethyl-8-phenyl-11-(9-phenyl-9H-carbazole). White powder of -3-yl)-8,13-dihydrobenzothieno[3,2-a]acridine (Compound 2) 10.8 g (yield 73%).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 1.

The following 32 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ (ppm) = 8.69 (1H)

8.43 (1H)

8.26 (1H)

7.96 (1H)

7.95 (1H)

7.65-7.80 (7H)

7.45-7.65 (10H)

7.25-7.35 (2H)

6.54 (1H)

6.23 (1H)

2.43 (6H)

<Example 2 (Synthesis of Compound 20)>

N-(9,9-Dimethyl-9H-indol-2-yl)-N-(13,13-dimethyl-8-phenyl-8,13-dihydrobenzothieno[3,2 -a] acridine-11-yl)-aniline synthesis;

The same procedure as in Example 1 was carried out to synthesize 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzothieno[3,2-a]acridine.

followed by

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Join

It was heated and stirred at 115 ° C for 1 hour. After cooling to room temperature, water and toluene were added, and the organic layer was collected by liquid separation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to give N-(9,9-dimethyl-9H-indol-2-yl)-N- (13, White powder of 13-dimethyl-8-phenyl-8,13-dihydrobenzothieno[3,2-a]acridin-11-yl)-phenylamine (Compound 20) 12.8 g (yield 89%).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 2 .

The following 38 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ(ppm)=8.51(1H)

7.91 (1H)

7.60-7.75 (4H)

7.56 (1H)

7.40-7.50 (6H)

7.20-7.48 (6H)

7.10-7.20 (2H)

7.06 (1H)

6.96 (1H)

6.71 (1H)

6.51 (1H)

6.09 (1H)

2.20 (6H)

1.43(6H)

<Example 3 (Synthesis of Compound 27)>

8-(9,9-Dimethyl-9H-indol-2-yl)-13,13-dimethyl-11-(9-phenyl-9H-indazol-3-yl)-8,13- Synthesis of dihydrobenzothieno[3,2-a]acridine;

The same procedure as in Example 1 was carried out to synthesize 11-bromo-8-(9,9-dimethyl-9H-indol-2-yl)-13,13-dimethyl-8,13-dihydrobenzothiophene. [3,2-a] acridine.

followed by

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. Add ruthenium (triphenylphosphine) Palladium 0.2 g was heated and stirred at 72 ° C for 18 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to give 8-(9,9-dimethyl-9H-indol-2-yl)-13,13- White powder of methyl-11-(9-phenyl-9H-indazol-3-yl)-8,13-dihydrobenzothieno[3,2-a]acridine (Compound 27) 2.8 g (Yield 72%).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 3.

The following 40 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ(ppm)=8.70(1H)

8.44 (1H)

8.26 (1H)

8.13 (1H)

7.90-8.00 (3H)

7.63-7.75 (5H)

7.38-7.63 (12H)

7.25-7.38 (2H)

6.66 (1H)

6.50 (1H)

2.45 (6H)

1.60(6H)

<Example 4 (Synthesis of Compound 4)>

13,13-Dimethyl-8-phenyl-11-(9-phenyl-9H-indazol-3-yl)-8,13-dihydrobenzofuro[3,2-a]acridine Synthesis

In the same manner as in Example 1, 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzofuro[3,2-a]acridine was synthesized.

followed by

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.8 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 72 ° C for 3 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 13,13-dimethyl-8-phenyl-11-(9-phenyl-9H-carbazole). White powder of -3-yl)-8,13-dihydrobenzofuro[3,2-a]acridine (Compound 4) 11.3 g (yield 84%).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 4.

The following 32 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ (ppm) = 8.42 (1H)

8.38 (1H)

8.26 (1H)

7.93 (1H)

7.20-7.80 (20H)

6.48 (1H)

6.23 (1H)

2.32 (6H)

<Example 5 (Synthesis of Compound 25)>

N-(9,9-Dimethyl-9H-indol-2-yl)-N-(13,13-dimethyl-8-phenyl-8,13-dihydrobenzofuran[3,2 -a] acridine-11-yl)-aniline synthesis;

The same procedure as in Example 1 was carried out to synthesize 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzofuro[3,2-a]acridine.

will

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Join

It was heated and stirred at 115 ° C for 1 hour. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to give N-(9,9-dimethyl-9H-indol-2-yl)-N- (13, White powder 9.5 g of 13-dimethyl-8-phenyl-8,13-dihydrobenzofuro[3,2-a]acridin-11-yl)-phenylamine (Compound 25) 66%).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 5.

The following 38 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ(ppm)=8.21(1H)

6.90-7.75 (22H)

6.71 (1H)

6.43 (1H)

6.09 (1H)

2.10 (6H)

1.43(6H)

<Example 6 (Synthesis of Compound 41)>

Synthesis of 13,13-dimethyl-8-phenyl-11-(9H-carbazol-9-yl)-8,13-dihydrobenzofuro[3,2-a]acridine;

In the same manner as in Example 1, 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzofuro[3,2-a]acridine was synthesized.

will

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Join

The mixture was heated and stirred at 115 ° C for 1 hour. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to give 13,13-dimethyl-8-phenyl-11-(9H-carbazol-9-yl) 8.5 g (yield 68%) of white powder of -8,13-dihydrobenzofuro[3,2-a]acridine (Compound 41).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 6.

The following 28 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ(ppm)=8.29(1H)

8.18 (2H)

7.10-7.80 (17H)

6.52 (1H)

6.38 (1H)

2.28 (6H)

<Example 7 (Synthesis of Compound 42)>

13,13-Dimethyl-8-phenyl-11-(3,3-dimethyl-1-phenyl-1,3-dihydroindeno[2,1-b]oxazol-10-yl Synthesis of-8,13-dihydrobenzofuro[3,2-a]acridine;

The same procedure as in Example 1 was carried out to synthesize 11-bromo-13,13-dimethyl-8-phenyl-8,13-dihydrobenzofuro[3,2-a]acridine.

will

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 72 ° C for 5 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 13,13-dimethyl-8-phenyl-11-(3,3-dimethyl-1) -phenyl-1,3-dihydroindeno[2,1-b] White powder 8.7 g (yield 77%) of oxazol-10-yl)-8,13-dihydrobenzofuro[3,2-a]acridine (Compound 42).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 7.

The following 40 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ (ppm) = 8.64 (1H)

8.51 (1H)

8.38 (1H)

7.98 (1H)

7.92 (1H)

7.20-7.80 (21H)

6.49 (1H)

6.24 (1H)

2.35 (6H)

1.50 (6H)

<Example 8 (Synthesis of Compound 23)>

13,13-Dimethyl-8-(9,9-dimethyl-9H-indol-2-yl)-11-(9H-carbazol-9-yl)-8,13-dihydrobenzofuran And [3,2-a] acridine synthesis;

The same procedure as in Example 1 was carried out to synthesize 11-bromo-13,13-dimethyl-8-(9,9-dimethyl-9H-indol-2-yl)-8,13-dihydrobenzofuran. And [3,2-a] acridine.

11-Bromo-13,13-dimethyl-8-(9,9-dimethyl-9H-indol-2-yl)-8,13-dihydrobenzofuran

It was added to a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour.

Join

It was heated and stirred at 115 ° C for 1 hour. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude material. The crude material was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 13,13-dimethyl-8-(9,9-dimethyl-9H-indole-2- 11.5 g of white powder of 11-(9H-carbazol-9-yl)-8,13-dihydrobenzofuro[3,2-a]acridine (Compound 23) (yield 54%) ).

The structure was identified using NMR for the obtained white powder. ^The results of ¹ H-NMR measurement are shown in Fig. 8.

The following 36 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ).

δ (ppm) = 8.61 (1H)

8.12-8.20 (3H)

7.88-8.00 (2H)

7.77 (1H)

7.66 (1H)

7.35-7.60 (11H)

7.24 (2H)

7.16 (1H)

6.68 (1H)

6.50 (1H)

2.37 (6H)

1.60(6H)

<Example 9 (Measurement of glass transition point)>

The compounds having the acridine ring-ring structure obtained in Examples 1 to 8 were subjected to a high-sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100SA) to obtain a glass transition point. The results are as follows.

From this, it is understood that the compound of the present invention has a glass transition point of 100 ° C or more and exhibits a stable film state.

<Example 10 (evaluation of work function)>

Using the compounds obtained in Examples 1 to 8, a vapor deposited film having a thickness of 100 nm was formed on an ITO substrate, and the work function was measured by a free potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd., PYS-202 type).

From the above results, it is understood that the compound of the present invention exhibits an ideal energy level similarly to a work function of a general hole transporting material such as NPD or TPD of 5.54 eV, and has good hole transporting ability.

(Evaluation of characteristics of organic EL elements)

<Example 11>

An organic EL device having the structure shown in Fig. 9 having the hole transport layer 4 formed of the compound (compound 2) having an acridine ring structure obtained in Example 1 was produced. This organic EL element is formed by sequentially depositing an ITO electrode as a transparent anode 2 on the glass substrate 1, and sequentially depositing the hole injection layer 3, the hole transport layer 4, the light-emitting layer 5, the electron transport layer 6, and the electrons. The layer 7 and the cathode (aluminum electrode) 8 were implanted.

Specifically, the glass substrate 1 on which the ITO having a film thickness of 150 nm was formed was washed with an organic solvent, and then the surface was washed with oxygen plasma. Thereafter, the glass substrate 1 with the ITO electrode was mounted in a vacuum vapor deposition machine, and the pressure inside the vapor deposition machine was reduced to 0.001 Pa or less. Then, the hole injection layer 3 having a film thickness of 20 nm was formed by coating the transparent anode 2 using the compound 57 of the following structural formula.

On the hole injection layer 3, the compound (Compound 2) of Example 1 was deposited to form a hole transport layer 4 having a film thickness of 40 nm.

On the hole transport layer 4, the compound 58 of the following structural formula and the compound 59 of the following structural formula were used, and the vapor deposition rate was double-evaporated at a vapor deposition rate of Compound 58: Compound 59 = 5:95. A light-emitting layer 5 having a film thickness of 30 nm was formed.

An electron transport layer 6 having a film thickness of 30 nm was formed on the light-emitting layer 5 using Alq ₃ .

An electron injecting layer 7 having a film thickness of 0.5 nm was formed on the electron transporting layer 6 using lithium fluoride.

Finally, aluminum was vapor-deposited to have a film thickness of 150 nm to form a cathode 8.

The organic EL device produced in the above manner was measured for the light-emitting characteristics when a DC voltage was applied at room temperature in the atmosphere. The results are shown in Table 1.

<Example 12>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 20) of Example 2 to form the hole transport layer 4. The luminescent properties of the organic EL device produced were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 13>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 27) of Example 3 to form the hole transport layer 4. The luminescent properties of the produced organic EL device were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 14>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 4) of Example 4 to form the hole transport layer 4. The luminescent properties of the organic EL device produced were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 15>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 25) of Example 5 to form the hole transport layer 4. The luminescent properties of the produced organic EL device were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 16>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 41) of Example 6 to form the hole transport layer 4. The luminescent properties of the produced organic EL device were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 17>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 42) of Example 7 to form the hole transport layer 4. The luminescent properties of the organic EL device produced were measured in the same manner as in Example 11. The results are shown in Table 1.

<Example 18>

An organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound (Compound 23) of Example 8 to form the hole transport layer 4. The luminescent properties of the produced organic EL device were measured in the same manner as in Example 11. The results are shown in Table 1.

<Comparative Example 1>

For comparison, an organic EL device was produced under the same conditions as in Example 11 except that the compound (Compound 2) of Example 1 was replaced with the compound 60 of the following structural formula to form the hole transport layer 4. The luminescent properties of the organic EL device produced were measured in the same manner as in Example 11. The results are shown in Table 1.

As shown in Table 1, the driving voltage at a current having a current density of 10 mA/cm ² was 5.17 V for the organic EL device of Comparative Example 1, and the organic EL device of the compound of Examples 1 to 8 of the present invention was 4.70. ~5.05V, which is a lower voltage. In addition, regarding the electric power efficiency, the electric efficiency of the organic EL element of Comparative Example 1 was 5.49 lm/W, and the organic EL elements of the compounds of Examples 1 to 8 of the present invention were 5.91 to 6.78 lm/W, both of which were greatly improved.

From the above results, it is understood that the organic EL device using the compound having the acridine ring-ring structure of the present invention can achieve an improvement in power efficiency or a decrease in the practical driving voltage as compared with the organic EL device using the known material compound 60.

[Industry Utilization]

The compound having an acridine ring-ring structure of the present invention has a high hole transporting ability, excellent electron blocking ability, excellent amorphousness, and stable film state, so that it is a compound for an organic EL device. excellent. By using the compound to produce an organic EL device, high luminous efficiency and power efficiency can be obtained, and the practical driving voltage can be lowered to improve durability. For example, it can be used for household electrical products or lighting.

Claims (12)

a compound having an acridine full ring structure represented by the following formula (1); In the formula, X represents an oxygen atom or a sulfur atom, and R ¹ to R ⁹ represent a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 5~ a cycloalkyl group of 10, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensation a polycyclic aromatic group or an aryloxy group, and may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; R ¹⁰ and R ¹¹ are an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, and an aromatic group a heterocyclic group, a condensed polycyclic aromatic group or an aryloxy group, and may also be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; Ar ¹ , Ar ² , Ar ³ represent an aromatic group a hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, and Ar ² and Ar ³ may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring; A represents an aromatic hydrocarbon, Aromatic heterocyclic or condensed The divalent aromatic group, or a single bond, and A is an aromatic hydrocarbon in the aromatic heterocyclic or the condensed polycyclic aromatic divalent group, A and Ar ² may be via a single bond or a methylene group, Oxygen atoms or sulfur atoms are bonded to each other to form a ring. A compound having an acridine ring-ring structure according to the first aspect of the patent application, wherein, for the benzene ring having an A bond, R ¹ , R ² , R ³ and A are represented by the following formula (1-1) Bonding In the formula, X, R ¹ to R ¹¹ , Ar ¹ , Ar ² , Ar ³ and A have the same meanings as described in the above formula (1). A compound having an acridine ring-ring structure according to claim 1 or 2, wherein the A-based aromatic hydrocarbon or the condensed polycyclic aromatic divalent group. A compound having an acridine ring-ring structure according to item 3 of the patent application, wherein A is a divalent group of an aromatic hydrocarbon or a condensed polycyclic aromatic ring represented by the following formula (2); Wherein r ¹² represents an integer of 0 to 4, and R ¹² is a halogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. , an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group Or an aryloxy group or a linking group, and when a plurality of R ¹² are present, a plurality of R ¹² may be bonded to each other to form a ring. A compound having an acridine ring-ring structure according to item 4 of the patent application, wherein A is a divalent group of an aromatic hydrocarbon or a condensed polycyclic aromatic ring represented by the following formula (2 ' ); In the formula, r ¹² and R ¹² have the same meanings as described in the formula (2). a compound having an acridine ring-ring structure according to item 5 of the patent application, which is represented by the following formula (1-2); In the formula, X, R ¹ to R ¹¹ , Ar ¹ , Ar ³ and A have the same meanings as defined in the formula (1) or (1-1), and Ar ⁴ represents the formula (1) or (1). -1) The divalent group of the group of Ar ² described, and Ar ³ and Ar ⁴ may be bonded to each other via a single bond or a methylene group, an oxygen atom or a sulfur atom to form a ring. A compound having an acridine ring-ring structure as claimed in claim 1 or 2, wherein A is a single bond. An organic electroluminescence device having a pair of electrodes and at least one organic layer sandwiched between the pair of electrodes, characterized in that a compound having an acridine ring-ring structure as in the first aspect of the patent application is used as the organic compound The constituent materials of the layer. The organic electroluminescence device of claim 8, wherein the organic layer is a hole transport layer. The organic electroluminescent device of claim 8, wherein the organic layer is an electron blocking layer. The organic electroluminescence device of claim 8, wherein the organic layer is a hole injection layer. The organic electroluminescence device of claim 8, wherein the organic layer is a light-emitting layer.