TW201434819A - Compound having indenoacridan ring structure, and organic electroluminescent device - Google Patents

Abstract

An organic compound with excellent characteristics excelling in hole injecting and transporting performance and having an electron-blocking ability, high stability in a thin film state and excellent heat resistance is provided as a material for an organic electroluminescent device of high efficiency and high durability, and the organic electroluminescent device of high luminous efficiency and high durability is provided using this compound. The compound having an indenoacridan ring structure is represented by a general formula (1), and the organic electroluminescent device having a pair of electrodes and at least one organic layer sandwitched there between is characterized in that the compound is used as a constitutive material of at least one organic layer in the organic electroluminescent device.

Description

Compound having an indole acridine ring structure and an organic electroluminescence device

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 indole acridine ring-filled structure and an organic electricity using the same Photoluminescent element.

Since the organic electroluminescence device is a self-luminous element, it is brighter than the liquid crystal element and has excellent visibility, and can be vividly displayed, and has 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 people laminate a phosphor capable of transporting electrons, argon (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) and an aromatic amine compound capable of transporting holes, and inject a charge therebetween. among the light-emitting phosphor layer, and a voltage of 10V or less is obtained 1000cd / m ² or more high brightness (for example, see 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 by sequentially providing an anode, a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on a substrate. The electric field light-emitting element of the electron injecting layer or the cathode can achieve high efficiency and durability (for example, refer to Non-Patent Document 1).

In addition, attempts have been made to utilize triplet excitons in order to further improve luminous efficiency, and the use of phosphorescent emitters has also been studied (for example, refer to Non-Patent Document 2).

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. As described in the above Non-Patent Document 2, the selection of the organic material in the organic electroluminescence device has a significant influence on characteristics such as efficiency and durability of the device.

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 deteriorated by crystallization under high temperature conditions (see, for example, Non-Patent Document 3). 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, improvement in amorphousness is sought, and at the same time, driving voltage is lower, or luminous efficiency is higher.

[Previous Technical Literature]

[Patent Literature]

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

[Patent Document 2] Patent No. 3194657

Patent Document 3: WO2006/033563

Patent Document 4: WO2007/110228

Patent Document 5: WO2010/147319

[Non-patent literature]

[Non-Patent Document 1] Proceedings of the 9th Workshop of the Applied Physics Society, 55~61 (2001)

[Non-Patent Document 2] Proceedings of the 9th Workshop of the Applied Physics Society, 23~31 (2001)

[Non-Patent Document 3] Proceedings of the Third Regular Meeting of the Organic EL Symposium, 13~14 (2006)

[Non-Patent Document 4] J. Org. Chem., 60, 7508 (1995)

[Non-Patent Document 5] Synth. Commun., 11, 513 (1981)

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. A characteristic organic compound, and the use of this compound provides an organic electroluminescent element of high efficiency and high durability.

The physical properties of the organic compound to be provided by the present invention include: (1) good hole injection characteristics, (2) large mobility of the hole, (3) excellent electron blocking ability, and (4) stability of the film state, (5) Excellent heat resistance. Moreover, the physical characteristics of the organic electroluminescent element to be provided by the present invention include, for example, (1) high luminous efficiency and power efficiency, (2) low light-emission starting voltage, and (3) low practical driving voltage.

In order to achieve the above object, the inventors of the present invention expect that the aromatic tertiary amine structure has a high hole injection, a transporting ability, and an electron-blocking property of the anthracycline-filled ring structure, and the secondary structure has heat resistance and stability to the film. The effect of the properties was to design and chemically synthesize a compound having an indole acridine ring-filled structure, and various organic electroluminescence elements were tried by using the compound, and the characteristics of the elements were evaluated. As a result, the present invention was completed.

1) That is, the present invention is a compound having an indolo-acrididine ring-ring structure represented by the following formula (1).

(wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, or a single bond, and B represents A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a vinyl group which may have a substituent, selected from aromatic a disubstituted amino group substituted with a group in a hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group. R ₁ to R ₁₀ may be the same or different and are a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom or a cyanogen. a base, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom which may have a substituent 5 to 10 cycloalkyloxy, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic rings a condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom. The ring forms a ring. R ₁₁ to R ₁₄ may be the same or different, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and may have a substituent having 5 to 5 carbon atoms. a cycloalkyl group of 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched alkane having 1 to 6 carbon atoms which may have a substituent An oxy group, a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed group which may have a substituent a polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom, and R ₁₁ and R ₁₂ , R ₁₃ and R _{14 are each a} single bond. Bonded to each other to form a ring. Here, A is a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted An unsubstituted condensed polycyclic aromatic divalent group, and B is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group Or a vinyl group having a substituent, a disubstituted amine group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, or A and B may be intervened. A bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom is bonded to each other to form a ring.

2) Further, the present invention is a compound having an indolo-acridin ring-ring structure as in the above 1), which is represented by the following formula (1-1).

(wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ and Ar ₂ may be used. The same or different, which means a vinyl group which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. Alternatively, Ar ₁ and Ar ₂ may be bonded to each other by a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. R ₁ to R ₁₀ may be the same or different and are a hydrogen atom or a ruthenium. An atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom number of 5 to 10 which may have a substituent. a cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent. a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, substituted or a substituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be a single bond, a substituted or unsubstituted methylene group, or an oxygen group. The atom or the sulfur atom is bonded to each other to form a ring. R ₁₁ to R ₁₄ may be the same or different, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and may have a substituent. a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear chain having 1 to 6 carbon atoms which may have a substituent Alkoxy group or branched, a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted group a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, or a methylene group in which R ₁₁ and R ₁₂ , R ₁₃ and R _{14 are each a} single bond, substituted or unsubstituted , an oxygen atom or a sulfur atom bonded to each other to form a ring. in this case, A and Ar ₁ can also be interposed a single bond, the substituted or unsubstituted methylene group, an oxygen atom A sulfur atom bonded to each other to form a ring.)

3) The present invention is a compound having an indolo-acridin ring-ring structure as in the above 1), wherein, in the above formula (1), A is a substituted or unsubstituted aromatic hydrocarbon or substituted or unsubstituted The condensed polycyclic aromatic divalent group.

Further, the present invention is a compound having an indolo-acridin ring-ring structure as in the above 3), wherein, in the above formula (1), A is taken from a substituted or unsubstituted benzene to remove two hydrogen atoms. The two-valent base.

5) The present invention is a compound having an indolo-acridin ring-ring structure as in the above 3), wherein, in the above formula (1), A is taken from a substituted or unsubstituted biphenyl to remove two hydrogen atoms. The two-valent base.

6) The present invention is a compound having an indolo-acridin ring-ring structure as in the above 1), wherein, in the above formula (1), A is taken from a substituted or unsubstituted oxime to take two hydrogen atoms. The two-valent base.

Further, the present invention is the compound having the indole acridine ring-filled structure of the above 1), wherein, in the above formula (1), B is a substituted or unsubstituted carbazolyl group.

Further, the present invention is the compound having the indole acridine ring-filled structure of the above 1), wherein, in the above formula (1), B is a substituted or unsubstituted dibenzofuranyl group.

Further, the present invention is the compound having an indole acridine ring-filled structure as in the above 1), wherein, in the above formula (1), B is a substituted or unsubstituted phenyl group.

Further, the present invention is the compound having an indeno acridine ring-filled structure as in the above 1), wherein, in the above formula (1), B is a substituted or unsubstituted biphenyl group.

11) An organic electroluminescence device having a pair of electrodes and at least one organic layer sandwiched therebetween, characterized in that the one of the items 1) to 10) has an indolo-acridium ring-filled structure. The compound is used as a constituent material of at least one organic layer.

Further, the invention is the organic electroluminescence device according to the above 11), wherein the organic layer is a hole transport layer.

Further, the invention is the organic electroluminescence device according to the above 11), wherein the organic layer is an electron blocking layer.

Further, the invention is the organic electroluminescence device according to the above 11), wherein the organic layer is a hole injection layer.

Further, the invention is the organic electroluminescence device according to the above 11), wherein the organic layer is a light-emitting layer.

As a "substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring or a substituted or unsubstituted condensed polycyclic aromatic divalent aromatic group" represented by A in the general formula (1) "Aromatic hydrocarbons" or "aromatic hydrocarbons", "substituted or unsubstituted aromatic hydrocarbons" or "substituted or unsubstituted condensed polycyclic aromatics""cyclo" or "condensed polycyclic aromatic", specifically, benzene, biphenyl, terphenyl, biphenyl, styrene, naphthalene, anthracene, vinyl naphthalene, anthracene, phenanthrene, dihydroanthracene, anthracene , pyridine, pyrimidine, three , furan, piper, thiophene, anthracene, quinoline, isoquinoline, benzofuran, benzothiophene, porphyrin, carbazole, porphyrin, benzo Oxazole, benzothiazole, quinoxaline, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene, Pyridine, phenanthroline, acridine and the like.

Further, as the "valent group of the substituted or unsubstituted aromatic hydrocarbon" represented by A in the general formula (1), "the substituted or unsubstituted aromatic heterocyclic ring" or "substituted or The unsubstituted condensed polycyclic aromatic divalent group represents a divalent group obtained by taking two hydrogen atoms from the above-mentioned "aromatic hydrocarbon", "aromatic heterocyclic ring" or "condensed polycyclic aromatic".

Here, the "aromatic heterocyclic ring" in the "divalent group of the substituted or unsubstituted aromatic heterocyclic ring" is preferably a sulfur-containing aromatic such as thiophene, benzothiophene, benzothiazole or dibenzothiophene. Heterocycle, or furan, piper, benzofuran, benzo An oxygen-containing aromatic heterocyclic ring such as oxazole or dibenzofuran, an anthracene or a carbazole is preferred.

As the A in the formula (1), it is preferably a "valent group of a substituted or unsubstituted aromatic hydrocarbon", a "substituted or unsubstituted condensed polycyclic aromatic divalent group", hydrazine or The carbazole is obtained by taking two hydrogen atoms to obtain a divalent group, and in particular, a divalent group obtained by taking two hydrogen atoms from benzene, biphenyl or hydrazine is preferred.

As a "substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring or a substituted or unsubstituted condensed polycyclic aromatic divalent aromatic group" represented by A in the general formula (1) Specific examples of the "substituent" of the "substituted aromatic hydrocarbon", the "substituted aromatic heterocyclic ring" or the "substituted condensed polycyclic aromatic ring" include a halogen atom, a cyano group, a nitro group, a fluorine atom and a chlorine atom. a halogen atom such as a bromine atom or an iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and hexyl a linear or branched alkyl group having 1 to 6 carbon atoms; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; An alkenyl group such as a propyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group or An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, or triphenylene; pyridyl and thio Benzyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, oxazolyl, benzo Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a group such as an indenyl group such as an ethyl fluorenyl group or a benzhydryl group; and the substituents may be further substituted with the substituents exemplified above.

Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

"Substituted or unsubstituted aromatic hydrocarbon group" represented by B in the formula (1), "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensed polycyclic aromatic group" In the "aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group", specific examples thereof include a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an anthracenyl group, and a phenanthrene group. Base, fluorenyl, fluorenyl, fluorenyl, fluorenyl, allyldienyl, hydrazine, pyridyl, furyl, pyrrolyl, thienyl, quinolinyl, isoquinolinyl, benzo Furanyl, benzothienyl, fluorenyl, carbazolyl, benzo An azolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a porphyrin group, and the like.

Specific examples of the "substituent" in the "substituted aromatic hydrocarbon group", the "substituted aromatic heterocyclic group" or the "substituted condensed polycyclic aromatic group" represented by B in the formula (1) include a ruthenium atom. , cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom or iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, positive a linear or branched alkyl group having 1 to 6 carbon atoms such as a pentyl group, an isopentyl group, a neopentyl group or a n-hexyl group; and a carbon number of 1 to 6 such as a methoxy group, an ethoxy group or a propoxy group; a linear or branched alkoxy group; an allyl group such as an allyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an aralkoxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group and a biphenyl group; An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a triphenylene, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group or a bis-phenylene group. ; pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a group such as an indenyl group such as an ethenyl group or a benzamidine group; and the substituents may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The "aromatic hydrocarbon group" in the "disubstituted amine group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group" represented by B in the formula (1), Specific examples of the "aromatic heterocyclic group" or the "condensed polycyclic aromatic group" include "substituted or unsubstituted aromatic hydrocarbon group" represented by B in the above formula (1), "substituted or "Aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group" in the "unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensed polycyclic aromatic group" For the same foundation. Further, the substituent may have a substituent, and the substituent may be a "substituent" listed above with respect to the above "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" or "substituted condensed polycyclic aromatic group". For the same person, the ideal one can also enumerate the same.

The "aromatic heterocyclic group" in the "substituted or unsubstituted aromatic heterocyclic group" of B in the formula (1) is preferably a thienyl group, a benzothienyl group, a benzothiazolyl group or a diphenyl group. Sulfur-containing aromatic heterocyclic group such as thienyl, furyl, piperidyl, benzofuranyl, benzo An oxygen-containing aromatic heterocyclic ring or an oxazolyl group such as an azole group or a dibenzofuranyl group is preferred.

As the B in the formula (1), it is preferably a "substituted or unsubstituted aromatic hydrocarbon group", a "substituted or unsubstituted condensed polycyclic aromatic group", and "selected from an aromatic hydrocarbon group or an aromatic group." A disubstituted amino group substituted with a heterocyclic group or a condensed polycyclic aromatic group, a carbazolyl group, a dibenzofuranyl group, or a dibenzothiophene group, particularly a "substituted or unsubstituted aromatic group" "hydrocarbyl group", "substituted or unsubstituted condensed polycyclic aromatic group", "disubstituted amine group substituted with a group selected from an aromatic hydrocarbon group or a condensed polycyclic aromatic group", carbazolyl, or diphenyl And furanyl is preferred.

Further, A and B in the formula (1) may be bonded directly or via a respective substituent to form a ring. In this case, it is preferred to separate a single bond, or a substituted or unsubstituted methylene group or an oxygen atom. Or a sulfur atom bond, more preferably a substituted or unsubstituted methylene group to form a ring.

The "alkyl group having a linear or branched carbon number of 1 to 6 which may have a substituent" represented by R ₁ to R ₁₀ in the formula (1), and the number of carbon atoms which may have a substituent "5 to 10 cycloalkyl groups" or "linear or branched alkenyl groups having 2 to 6 carbon atoms having a substituent", "linear or branched carbon atoms of 1 to 6""Alkylgroup","cycloalkyl group having 5 to 10 carbon atoms" or "linear or branched alkenyl group having 2 to 6 carbon atoms", specifically, methyl, ethyl or n-propyl group , isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantane Base, vinyl, allyl, isopropenyl, 2-butenyl and the like. Further, the groups may be bonded to each other by a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The "alkyl group having a linear or branched carbon number of 1 to 6 having a substituent" represented by R ₁ to R ₁₀ in the formula (1), and the number of carbon atoms having a substituent of 5 to 10 Examples of the "substituent" in the cycloalkyl group or the "linear or branched alkenyl group having 2 to 6 carbon atoms having a substituent" include a halogen atom, a cyano group, and a nitro group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; and an alkenyl group such as an allyl group; An aryloxy group such as a phenoxy group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an anthracenyl group, a phenanthryl group An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a mercapto group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group or a bis-phenylene group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinolyl group, or a different group Quinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo a group such as an azole group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a porphyrin group; The substituent may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the R ₁ to R ₁₀ in the formula (1), "a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent" or "a carbon atom which may have a substituent" In the cycloalkyloxy group of 5 to 10, "a linear or branched alkoxy group having 1 to 6 carbon atoms" or "a cycloalkoxy group having 5 to 10 carbon atoms" may specifically Listed are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy, cyclo Heptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the R ₁ to R ₁₀ in the formula (1), the "linear or branched alkoxy group having 1 to 6 carbon atoms having a substituent" or "the number of carbon atoms having a substituent of 5 to 10" Specific examples of the "substituent" in the cycloalkyloxy group include a halogen atom, a cyano group, a nitro group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methoxy group and an ethoxy group. a linear or branched alkoxy group having 1 to 6 carbon atoms such as a propoxy group; an alkenyl group such as an allyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; a benzyloxy group or a phenethyloxy group; Aralkyloxy; phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthryl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl Equivalent aromatic hydrocarbon group or condensed polycyclic aromatic group; pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, anthracenyl, oxazolyl Benzo a group such as an azole group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a porphyrin group; The substituent may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₁ to R ₁₀ in the formula (1), "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensation" Specific examples of the "aromatic hydrocarbon group", the "aromatic heterocyclic group" or the "condensed polycyclic aromatic group" in the cyclic aromatic group include a phenyl group, a biphenyl group, a biphenyl group, and a naphthyl group. Indenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl, pyridyl, furyl, pyrrolyl, thienyl, quinolinyl, isoquinoline Base, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo An azolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a porphyrin group, and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The "substituent" in the "substituted aromatic hydrocarbon group", the "substituted aromatic heterocyclic group" or the "substituted condensed polycyclic aromatic group" represented by R ₁ to R ₁₀ in the formula (1), specifically A halogen atom such as a halogen atom, a cyano group or a nitro group; a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a third group; a linear or branched alkyl group having 1 to 6 carbon atoms such as butyl, n-pentyl, isopentyl, neopentyl or n-hexyl; a carbon atom such as a methoxy group, an ethoxy group or a propoxy group; a linear or branched alkoxy group of 1 to 6; an alkenyl group such as an allyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; An aromatic hydrocarbon group such as a biphenyl group, a triphenylene group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, an anthracenyl group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group, or a triphenylene group, or a condensation Cycloalkyl; pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a group such as an anthracenyl group such as an ethenyl group or a benzamidine group; and the substituents may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the "aryloxy group" in the "substituted or unsubstituted aryloxy group" represented by R ₁ to R ₁₀ in the formula (1) include a phenoxy group, a biphenyloxy group, and a hydrazine group. Phenoxy, naphthyloxy, anthracenyloxy, phenanthrenyloxy, decyloxy, decyloxy, decyloxy, decyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the "substituent" in the "substituted aryloxy group" represented by R ₁ to R ₁₀ in the formula (1) include a halogen atom, a cyano group, and a nitro group; a fluorine atom, a chlorine atom, and a bromine atom; a halogen atom such as an iodine atom; a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl or n-hexyl a linear or branched alkyl group having 1 to 6 atoms; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; an allyl group or the like An alkenyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an anthracenyl group, An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a mercapto group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group or a bis-phenylene group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinoline group Base, isoquinolyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a group such as an anthracenyl group such as an ethenyl group or a benzamidine group; and the substituents may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent as represented by R ₁₁ to R ₁₄ in the formula (1), and the number of carbon atoms which may have a substituent "5 to 10 cycloalkyl groups" or "linear or branched alkenyl groups having 2 to 6 carbon atoms having a substituent", "linear or branched carbon atoms of 1 to 6""Alkylgroup","cycloalkyl group having 5 to 10 carbon atoms" or "linear or branched alkenyl group having 2 to 6 carbon atoms", specifically, methyl, ethyl or n-propyl group , isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantane Base, vinyl, allyl, isopropenyl, 2-butenyl and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The "linear or branched alkyl group having 1 to 6 carbon atoms having a substituent" represented by R ₁₁ to R ₁₄ in the formula (1), and the number of carbon atoms having a substituent of 5 to 10 Examples of the "substituent" in the cycloalkyl group or the "linear or branched alkenyl group having 2 to 6 carbon atoms having a substituent" include a halogen atom, a cyano group, and a nitro group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; and an alkenyl group such as an allyl group; An aryloxy group such as a phenoxy group or a tolyloxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an anthracenyl group, a phenanthryl group An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a mercapto group, a fluorenyl group, a fluorenyl group, a propadienyl fluorenyl group or a bis-phenylene group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinolyl group, or a different group Quinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo a group such as an azole group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a porphyrin group; The substituent may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, or the carbon atom which may have a substituent, represented by R ₁₁ to R ₁₄ in the formula (1) In the cycloalkyloxy group of 5 to 10, "a linear or branched alkoxy group having 1 to 6 carbon atoms" or "a cycloalkoxy group having 5 to 10 carbon atoms" may specifically Listed are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy, cyclo Heptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The linear or branched alkoxy group having 1 to 6 carbon atoms having a substituent represented by R ₁₁ to R ₁₄ in the formula (1) or the carbon atom having 5 to 10 having a substituent Specific examples of the "substituent" in the cycloalkyloxy group include a halogen atom, a cyano group, a nitro group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methoxy group and an ethoxy group. a linear or branched alkoxy group having 1 to 6 carbon atoms such as a propoxy group; an alkenyl group such as an allyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; a benzyloxy group or a phenethyloxy group; Aralkyloxy; phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthryl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl Equivalent aromatic hydrocarbon group or condensed polycyclic aromatic group; pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, anthracenyl, oxazolyl Benzo a group such as an azole group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a porphyrin group; The substituent may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₁₁ to R ₁₄ in the formula (1), "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensation" The "aromatic hydrocarbon group", the "aromatic heterocyclic group" or the "condensed polycyclic aromatic group" in the cyclic aromatic group, specifically, a phenyl group, a biphenyl group, a biphenyl group, a naphthyl group, Indenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, phenyl, pyridyl, furyl, pyrrolyl, thienyl, quinolinyl, isoquinoline Base, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzo An azolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a porphyrin group, and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

The "substituent" in the "substituted aromatic hydrocarbon group", the "substituted aromatic heterocyclic group" or the "substituted condensed polycyclic aromatic group" represented by R ₁₁ to R ₁₄ in the formula (1), specifically A halogen atom such as a halogen atom, a trifluoromethyl group, a cyano group or a nitro group; a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a different group; a linear or branched alkyl group having 1 to 6 carbon atoms such as butyl, tert-butyl, n-pentyl, isopentyl, neopentyl or n-hexyl; methoxy, ethoxy, propoxy a linear or branched alkoxy group having 1 to 6 carbon atoms; an alkenyl group such as an allyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; a phenoxy group or a tolyloxy group; Aryloxy; aralkyloxy, benzyloxy, etc.; phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a propadienyl fluorenyl group or a bis-phenylene group; a pyridyl group, a piperidyl group, a thienyl group, a furyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, Benzofuranyl Benzothienyl, indolyl, carbazolyl, benzo Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a mercapto group such as an ethyl fluorenyl group or a benzhydryl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; an aromatic hydrocarbon group or a condensation group such as a diphenylamino group or a naphthylamino group; a polycyclic aromatic group-substituted disubstituted amine group; a diarylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group or a dithienylamino group substituted with an aromatic heterocyclic group; a disubstituted amino group; a dienylamine group such as a diallylamino 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; A group such as a disubstituted amino group, which may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other to form a ring via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom.

Specific examples of the "aryloxy group" in the "substituted or unsubstituted aryloxy group" represented by R ₁₁ to R ₁₄ in the formula (1) include a phenoxy group, a biphenyloxy group, and a hydrazine group. Phenoxy, naphthyloxy, anthracenyloxy, phenanthrenyloxy, decyloxy, decyloxy, decyloxy, decyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the "substituent" in the "substituted aryloxy group" represented by R ₁₁ to R ₁₄ in the formula (1) include a halogen atom, a trifluoromethyl group, a cyano group, and a nitro group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl a linear or branched alkyl group having 1 to 6 carbon atoms such as n-hexyl; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; Alkenyl group; aryl group; aryloxy group; aryloxy group; aryloxy group; Aromatic hydrocarbon group or condensation such as phenyl, biphenyl, tert-triphenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, alkadienyl, hydrazine Polycyclic aromatic group; pyridyl, piperidyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzofuranyl, benzothienyl, fluorenyl, carbazolyl, benzene and Aromatic heterocyclic group such as azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, porphyrinyl; styryl, naphthyl An arylvinyl group such as a vinyl group; a mercapto group such as an ethyl fluorenyl group or a benzhydryl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; an aromatic hydrocarbon group or a condensation group such as a diphenylamino group or a naphthylamino group; a polycyclic aromatic group-substituted disubstituted amine group; a diarylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group or a dithienylamino group substituted with an aromatic heterocyclic group; a disubstituted amino group; a dienylamine group such as a diallylamino group; or a substituent substituted with an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, an aromatic heterocyclic group or an alkenyl group; Substituents such as substituted amine groups may be further substituted with the substituents exemplified above. Further, the substituents may be bonded to each other to form a ring via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom.

As the "substituted or unsubstituted aromatic hydrocarbon group" represented by Ar ₁ or Ar ₂ in the general formula (1-1), "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted" The "aromatic hydrocarbon group", the "aromatic heterocyclic group" or the "condensed polycyclic aromatic group" in the condensed polycyclic aromatic group are specifically represented by B in the above formula (1). "Aromatic hydrocarbon group" in "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensed polycyclic aromatic group", The aromatic heterocyclic group or the "condensed polycyclic aromatic group" is represented by the same group. Further, the substituent may have a substituent, and a "substituted aromatic hydrocarbon group", a "substituted aromatic heterocyclic group" or a "substituted aromatic heterocyclic group" represented by B in the above formula (1) may also be mentioned. The "substituents" of the "aromatic group" are listed as the same.

The "aromatic heterocyclic group" in the "substituted or unsubstituted aromatic heterocyclic group" represented by Ar ₁ or Ar ₂ in the formula (1-1) is preferably a thienyl group or a benzothienyl group. Sulfur-containing aromatic heterocyclic group such as benzothiazolyl or dibenzothiophenyl, furyl, piperidyl, benzofuranyl, benzo An oxygen-containing aromatic heterocyclic ring or an oxazolyl group such as an azole group or a dibenzofuranyl group is preferred.

As Ar ₁ and Ar ₂ in the formula (1-1), it is preferably a "substituted or unsubstituted aromatic hydrocarbon group", a "substituted or unsubstituted condensed polycyclic aromatic group", or a carbazolyl group. good.

Ar ₁ and Ar ₂ in the formula (1-1) may be bonded or form a ring directly or via a respective substituent, and in this case, a single bond, a substituted or unsubstituted methylene group is preferably interposed. Preferably, the oxygen atom or the sulfur atom is bonded, and more preferably, the substituted or unsubstituted methylene group is formed to form a ring.

Ar ₁ and A in the formula (1-1) may be bonded to form a ring directly or via a substituent of each of them, and in this case, a single bond, a substituted or unsubstituted methylene group is preferably interposed. Preferably, the oxygen atom or the sulfur atom is bonded, more preferably a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, and more preferably a substituted or unsubstituted methylene group. Form a ring.

The compound represented by the formula (1) of the present invention having an indolo-acridin ring-ring structure is a novel compound which has superior electron blocking ability and excellent amorphousness and film as compared with the conventional hole transporting material. The state is stable.

The compound having an indole acridine ring-filled structure represented by the formula (1) of the present invention can be used as a hole injection layer and/or a hole transport layer of an organic electroluminescence device (hereinafter simply referred to as an organic EL device). Material use. By using a hole having higher injectability than a conventional material, having a large mobility, a high electron blocking property, and a material having high electron stability, the generated excitons can be closed in the light-emitting layer, thereby further improving The opportunity of recombination of the hole and the electron can obtain high luminous efficiency, and at the same time, the driving voltage is lowered to improve the durability of the organic EL element.

The compound having an indole acridine ring-filled structure represented by the formula (1) of the present invention can also be used as a constituent material of an electron blocking layer of an organic EL device. By using a material having excellent electron blocking ability and superior in hole transportability of a conventional material and having high stability in a thin film state, high luminous efficiency, reduction in driving voltage, improvement in current resistance, and improvement of organic EL can be achieved. The role of the maximum luminous brightness of the component.

The compound having an indole acridine ring-filled structure represented by the formula (1) of the present invention can also be used as a constituent material of the light-emitting layer of the organic EL device. The material of the present invention which is superior in hole transportability to a conventional material and has a wide energy gap is used as a host material of the light-emitting layer, and is called a carrier material. As the light-emitting layer, the fluorescent light-emitting body or the phosphorescent light-emitting body of the dopant functions as an organic EL element capable of achieving a reduction in driving voltage and improved luminous efficiency.

The organic EL device of the present invention has a larger mobility and excellent electron blocking ability than the conventional hole transporting material, and has excellent amorphous properties and is stable with a film state. The compound is a full-ring structure, so high efficiency and high durability can be achieved.

The compound having an indole acridine ring-filled 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 element, and has excellent electron blocking ability and amorphous property. It is good, and the film state is stable and excellent in heat resistance. The luminous efficiency and electric power efficiency of the organic EL device of the present invention can reduce the practical driving voltage of the device. It can reduce the light-emitting start voltage 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

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

Fig. 2 shows a ¹ H-NMR chart of the compound (Compound 19) of Example 2 of the present invention.

Fig. 3 shows a ¹ H-NMR chart of the compound (Compound 30) of Example 3 of the present invention.

Fig. 4 shows a ¹ H-NMR chart of the compound (Compound 31) of Example 4 of the present invention.

Fig. 5 shows a ¹ H-NMR chart of the compound (Compound 32) of Example 5 of the present invention.

Fig. 6 shows a ¹ H-NMR chart of the compound (Compound 33) of Example 6 of the present invention.

Fig. 7 shows a ¹ H-NMR chart of the compound (Compound 34) of Example 7 of the present invention.

Fig. 8 is a view showing the configuration of EL elements of Examples 10 to 16 and Comparative Example 1.

The compound of the present invention having an indeno acridine ring-filled structure is a novel compound which can be synthesized, for example, in the following manner. For example, methyl 2-(9,9-dimethylinden-2-yl)aminobenzoate is synthesized by the reaction of methyl 2-aminobenzoate with 9,9-dimethyl-2-phosphonium iodide. And reacting with methyl magnesium chloride Synthesis of 2-{2-(9,9-dimethylindol-2-yl)amino)phenyl}propan-2-ol, cyclization to synthesize 7,7,13,13-tetramethyl- 7,13-Dihydro-5H-indolo[1,2-b]acridine. Then, the 7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine is condensed with an aryl halide by Buchwald-Hartwig reaction. In the reaction, a compound having an indolo-acrididine ring-ring structure of the present invention substituted with an aryl group at the 5-position can be synthesized.

Further, the introduction of the substituent into the indolo-acridinyl ring can be carried out, for example, by bromination using an indole acridine substituted with an aryl group at the 5-position, and synthesizing 2 by using N-bromosuccinate or the like. The brominated ruthenium and acridine derivatives are obtained, and the bromine substituents having different substitution positions are obtained by changing the reagents and conditions for bromination.

By performing a cross-coupling reaction such as Suzuki coupling of various boronic acids or boric acid esters (for example, refer to Non-Patent Document 4) (for example, refer to Non-Patent Document 5), it can be synthesized and introduced into an indole azide ring. A compound having an indolo-acridin ring-ring structure of the present invention having a substituent.

Among the compounds having an indeno acridine ring-filled structure represented by the formula (1), specific examples of the preferred compound are shown below, and the present invention is not limited to the compounds.

The purification of these compounds is carried out by column chromatography, adsorption purification using tannin extract, activated carbon, activated clay, etc., recrystallization by a solvent, crystallization, or the like. Identification of the compounds was carried out by NMR analysis. As the physical property value, the measurement of the glass transition point (Tg) and the work function was carried out. The glass transition point (Tg) is an indicator of the stability of the film state, and the work function is an indicator of the transportability of the hole.

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

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

The structure of the organic EL device of the present invention is, for example, sequentially composed of an anode, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, and a cathode on a substrate, and, for example, in an anode and a hole transport layer. A person having a hole injection layer therebetween and having an electron injection layer between the electron transport layer and the cathode. In the multilayer structure, several organic layers may be omitted. For example, the anode, the hole transport layer, the light-emitting layer, the electron transport layer, and the cathode may be sequentially provided on the substrate.

The anode of the organic EL device of the present invention may use an electrode material having a large work function such as ITO or gold. In the hole injection layer of the organic EL device of the present invention, in addition to the compound having an indole acridine ring-filled structure represented by the general formula (1) of the present invention, a polyporphyrin compound represented by beryllium cyanine can also be used. A material such as a starburst type triphenylamine derivative or various triphenylamine tetramers, an acceptor heterocyclic compound such as a hexacyanoazide heterotriphenyl compound or a coated polymer material. These materials may be formed into a film by a known method such as a spin coating method or an inkjet method, in addition to the vapor deposition method.

In the hole transporting layer of the organic EL device of the present invention, a compound having an indole acridine ring-filled structure represented by the formula (1) of the present invention can be used, and in addition, N,N'-diphenyl- can be used. N,N'-di(m-tolyl)-benzidine (hereinafter abbreviated as TPD) or N,N'-diphenyl-N,N'-bis(α-naphthyl)-benzidine (hereinafter abbreviated as NPD) , N, N, N', N'-tetraphenylbenzidine and other benzidine derivatives, 1,1-bis[(di-4-toluamino)phenyl]cyclohexane (hereinafter referred to as TAPC) ), various triphenylamine 3 polymers and 4 polymers. These may be formed separately, but may be mixed with other materials and formed into a single layer, or may be a laminated structure of layers formed separately, a laminated structure of layers in which the films are mixed, or A laminate structure in which a layer of a film is mixed with a layer formed separately. Further, as the injection hole and the transport layer of the hole, a coating type such as poly(3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT) / poly(styrenesulfonate) (hereinafter abbreviated as PSS) can be used. Polymer Materials. These materials may be formed into a film by a known method such as a spin coating method or an inkjet method, in addition to the vapor deposition method.

Further, in the hole injection layer or the hole transport layer, a material which is generally P-doped with tribromoaniline hexachloropyrene or the like, or a polymer compound having a TPD structure in the second structure may be used.

For the electron blocking layer of the organic EL device of the present invention, the general formula (1) of the present invention can be used. The compound having an indole acridine ring-filled structure may be used, in addition to 4,4',4"-tris(N-carbazolyl)amine (hereinafter abbreviated as TCTA), 9,9-bis [4- (carbazol-9-yl)phenyl]anthracene, 1,3-bis(carbazol-9-yl)benzene (hereinafter abbreviated as mCP), 2,2-bis(4-carbazol-9-ylphenyl) a carbazole derivative such as adamantane (hereinafter abbreviated as Ad-Cz), 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylindenyl)phenyl]- 9H-茀 is a compound having an electron blocking effect, such as a compound having a triphenylsulfonyl group and a triarylamine structure. These may be formed separately, but may be mixed with other materials and formed into a single layer. It may also be a laminated structure in which a layer of a single film-forming layer is laminated, a laminated structure in which the layers are formed into a film, or a layer in which a layer formed by mixing a film formed separately is formed. In addition to the method, a film can be formed by a known method such as a spin coating method or an inkjet method.

As the light-emitting layer of the organic EL device of the present invention, in addition to a metal complex of a quinolinol derivative such as Alq ₃ , various metal complexes, an anthracene derivative, a bisstyrylbenzene derivative, or the like may be used. Anthracene derivatives, An azole derivative, a poly-p-phenylene vinyl derivative, and the like. Further, the light-emitting layer may also be composed of a host material and a dopant material, and the host material is a compound having a fluorene-acridine ring-filled structure represented by the general formula (1) of the present invention, and the luminescent material may further use a thiazole derivative or a benzene. And imidazole derivatives, polydialkyl hydrazine derivatives and the like. Further, as the dopant material, quinacridone, coumarin, erythritol, hydrazine and derivatives thereof, benzopyran derivatives, rhodamine derivatives, and aminostyryl groups can be used. Derivatives, etc. These may be formed separately, but may be mixed with other materials and formed into a single layer, or may be a laminated structure of layers formed separately, a laminated structure of layers in which the films are mixed, or A laminate structure in which a layer of a film is mixed with a layer formed separately.

Further, as the luminescent material, a phosphorescent luminescent material can also be used. As the phosphorescent phosphor, a phosphorescent emitter of a metal complex such as ruthenium or platinum can be used. A green phosphor such as Ir(ppy) ₃ , a blue phosphor such as FIrpic or FIr6, a red phosphor such as Btp ₂ Ir(acac), or the like can be used, and the host material at this time is injected into the hole. As the host material for transportability, 4,4'-bis(N-carbazolyl)biphenyl (hereinafter abbreviated as CBP) or a carbazole derivative such as TCTA or mCP can be used, and the general formula of the present invention can be used. (1) A compound having an indole acridine ring-filled structure. As a host material for electron transportability, p-bis(triphenylsulfonyl)benzene (hereinafter abbreviated as UGH2), or 2,2',2"-(1,3,5-phenylene)-gin ( 1-phenyl-1H-benzimidazole (hereinafter abbreviated as TPBI) can produce a high-performance organic electroluminescence device.

The doping of the host material by the phosphorescent luminescent material is preferably in the range of 1 to 30% by weight for the entire light-emitting layer in order to avoid concentration extinction, and is preferably doped by co-evaporation.

These materials may be formed into a film by a known method such as a spin coating method or an inkjet method, in addition to the vapor deposition method.

As the hole blocking layer of the organic EL device of the present invention, a morpholine derivative such as Bathocuproin (hereinafter referred to as BCP) or bis(2-methyl-8-quinolinic acid)-4-benzene can be used. a metal complex of a quinolinol derivative such as aluminum(III)(a)(2-methyl-8-quinolinate)-4-phenylphenolate (hereinafter abbreviated as BAlq), and various rare earths can be used. Complex, triazole derivative, three derivative, A compound having a hole blocking effect such as an oxadiazole derivative. These materials can also serve as materials for the electron transport layer. These may be formed separately, but may be mixed with other materials and formed into a single layer, or may be a laminated structure of layers formed separately, a laminated structure of layers in which the films are mixed, or A laminate structure in which a layer of a film is mixed with a layer formed separately. These materials may be formed into a film by a known method such as a spin coating method or an inkjet method, in addition to the vapor deposition method.

As the electron transport layer of the organic EL device of the present invention, a metal complex of a quinolinol derivative such as Alq ₃ or BAlq can be used, and various metal complexes, triazole derivatives, and trisole can be used. derivative, Diazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinolin A morphine derivative, a phenanthroline derivative, a silole derivative or the like. These may be formed separately, but may be mixed with other materials and formed into a single layer, or may be a laminated structure of layers formed separately, a laminated structure of layers in which the films are mixed, or A laminate structure in which a layer of a film is mixed with a layer formed separately. These materials may be formed into a film by a known method such as a spin coating method or an inkjet method, in addition to the vapor deposition method.

As the electron injecting layer of the organic EL device of the present invention, an alkali metal salt such as lithium fluoride or cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, or a metal oxide such as alumina can be used, but electron transport is used. Ideal for layers and cathodes, they can also be omitted.

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

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

[Example 1]

<7,7,13,13-Tetramethyl-5-{4-(9-phenyl-9H-indazol-3-yl)phenyl}-7,13-dihydro-5H-indole[1 ,2-b] Synthesis of acridine (Compound 2) >

35.4 g of methyl 2-aminobenzoate, 50.0 g of 2-iodo-9,9-dimethyl-9H-indole, 22.51 g of sodium butoxide, and 500 ml of xylene were placed in a nitrogen-substituted reaction vessel. Nitrogen gas was introduced for 1 hour. 2.9 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 3.8 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and the mixture was stirred at 115 ° C for 5 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 product. The crude product was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to give 2-{(9,9-dimethyl-9H-indol-2-yl)amino}benzoic acid. The yellow powder of the methyl ester was 25.8 g (yield 48%).

31.0 g of methyl 2-{(9,9-dimethyl-9H-indol-2-yl)amino}benzoate and 310 ml of THF were added to a reaction vessel substituted with nitrogen, and methyl magnesium chloride was added dropwise. THF solution (3 mol/L) 108 ml. After stirring at room temperature for 1 hour, 300 ml of a 20% aqueous ammonium chloride solution was added, and extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2-[2-{(9,9-dimethyl-9H-indol-2-yl)amino}phenyl]propan-2-ol The pale yellow oil was 31.0 g (yield 100%).

31.0 g of 2-[2-{(9,9-dimethyl-9H-indol-2-yl)amino}phenyl]propan-2-ol and 62 ml of phosphoric acid were added to a reaction vessel substituted with nitrogen. The mixture was stirred at room temperature for 2 hours. After adding 300 ml of toluene and 300 ml of water and stirring, the precipitate was collected by filtration to obtain 7,7,13,13-tetramethyl-7,13-dihydro-5H- The pale yellow powder of indeno[1,2-b]acridine was 26.2 g (yield 89%).

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine 10.0 g, 3-(4-bromophenyl)-9- 8.2 g of phenyl-9H-carbazole, 3.6 g of sodium butoxide, and 100 ml of xylene were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and the mixture was stirred at 115 ° C for 2 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out to collect an organic layer. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene / n-hexane) to give 7,7,13,13-tetramethyl-5-{4-(9-phenyl-9H- 12.1 g (yield 75%) of a white powder of oxazol-3-yl)phenyl}-7,13-dihydro-5H-indeno[1,2-b]acridine (Compound 2).

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 38 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.65(1H), 8.28(1H), 8.11(2H), 7.88(1H), 7.86(1H), 7.60-7.70(5H), 7.35-7.60(7H), 7.20-7.35(3H) 7.12 (1H), 6.80-7.00 (2H), 6.53 (1H), 6.38 (1H), 1.76 (6H), 1.27 (6H).

[Example 2]

<7,7,13,13-Tetramethyl-5-{4-(dibenzofuran-4-yl)phenyl}-7,13-dihydro-5H-indole[1,2-b] Synthesis of acridine (Compound 19) >

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine 10.0 g, 4-(4-bromophenyl) synthesized in Example 1. 10.9 g of dibenzofuran, 3.6 g of sodium butoxide, and 100 ml of xylene were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and stirred at 115 ° C for 3 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene/n-hexane) to obtain 7,7,13,13-tetramethyl-5-{4-(dibenzofuran-4- Phenyl}-7,13-dihydro-5H-indolo[1,2-b]acridine (compound) 19) White powder 13.9 g (yield 80%).

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 33 hydrogen signals were detected in ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.37(2H), 8.05-8.15(2H), 7.85-7.95(2H), 7.62-7.72(2H), 7.45-7.62(5H), 7.40(1H), 7.31(1H), 7.23( 1H), 7.12 (1H), 6.88-7.02 (2H), 6.53 (1H), 6.41 (1H), 1.76 (6H), 1.27 (6H).

[Example 3]

<7,7,13,13-Tetramethyl-5-(p-triphenyl-3-yl)-7,13-dihydro-5H-indeno[1,2-b]acridine (Compound 30) Synthesis >

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine synthesized in Example 1 9.0 g, 3-bromo-p-triphenyl 10.0 g Sodium tert-butoxide 3.2 g and xylene (90 ml) were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of bis(dibenzylideneacetone)dipalladium(0) and 1.4 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and stirred at 115 ° C for 3 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 7,7,13,13-tetramethyl-5-(p-triphenyl-3-yl)-7 13.3 g (yield 80%) of white powder of 13-dihydro-5H-indolo[1,2-b]acridine (Compound 30).

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 35 hydrogen signals were detected in ¹ H-NMR (THF-d ₈ ). δ(ppm)=7.95(1H), 7.90(1H), 7.60-7.88(9H), 7.50(1H), 7.36-7.48(3H), 7.28-7.37(2H), 7.22(1H), 7.13(1H) , 6.85-7.00 (2H), 6.48 (1H), 6.36 (1H), 1.76 (6H), 1.27 (6H).

[Embodiment 4]

<7,7,13,13-tetramethyl-5-{3-(dibenzofuran-4-yl)phenyl}-7,13-dihydro-5H-indole Synthesis of [1,2-b]acridine (Compound 31) >

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine 10.0 g, 4-(3-bromophenyl) synthesized in Example 1. 10.9 g of dibenzofuran, 3.6 g of sodium butoxide, and 100 ml of xylene were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and the mixture was stirred at 115 ° C for 2 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 7,7,13,13-tetramethyl-5-{3-(dibenzofuran-4- 12.2 g (yield 70%) of a white powder of phenyl}-7,13-dihydro-5H-indeno[1,2-b]acridine (Compound 31).

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 33 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.25(1H), 8.00-8.10(3H), 7.81-7.92(2H), 7.77(1H), 7.69(1H), 7.57(1H), 7.40-7.52(4H), 7.28-7.39( 2H), 7.24 (1H), 7.13 (1H), 6.85-7.00 (2H), 6.57 (1H), 6.44 (1H), 1.76 (6H), 1.27 (6H).

[Embodiment 5]

<7,7,13,13-Tetramethyl-5-(p-triphenyl-4-yl)-7,13-dihydro-5H-indeno[1,2-b]acridine (Compound 32) Synthesis >

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine synthesized in Example 1 9.0 g, 4-bromo-p-triphenyl 10.0 g Sodium tert-butoxide 3.2 g and xylene (90 ml) were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.4 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and the mixture was stirred at 115 ° C for 2 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 7,7,13,13-tetramethyl-5-(p-triphenyl-4-yl)-7 White powder of 13-dihydro-5H-indeno[1,2-b]acridine (Compound 32) 12.6 g (yield 82%).

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 35 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.08(2H), 7.88-7.94(3H), 7.76-7.84(2H), 7.67-7.76(3H), 7.40-7.52(5H), 7.28-7.38(2H), 7.22(1H), 7.13 (1H), 6.83-6.98 (2H), 6.48 (1H), 6.36 (1H), 1.76 (6H), 1.27 (6H).

[Embodiment 6]

<7,7,13,13-Tetramethyl-5-(1-phenylindol-4-yl)-7,13-dihydro-5H-indolo[1,2-b]acridine (compound) 33) Synthesis >

7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine 10.0 g, 4-bromo-1-phenylindole synthesized in Example 1.哚 9.3 g, 3.6 g of sodium butoxide, and 100 ml of xylene were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and the mixture was stirred at 115 ° C for 5 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene / n-hexane) to give 7,7,13,13-tetramethyl-5-(1-phenylindole-4-yl 70.7 g (yield 67%) of white powder of -7,13-dihydro-5H-indolo[1,2-b]acridine (Compound 33).

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 32 hydrogen signals were detected in ¹ H-NMR (THF-d ₈ ). δ(ppm)=7.90(1H), 7.79(1H), 7.32-7.70(9H), 7.28(1H), 7.20(2H), 7.11(1H), 6.80-6.90(2H), 6.44(1H), 6.35 (1H), 6.22 (1H), 1.76 (6H), 1.15 (6H).

[Embodiment 7]

<7,7,13,13-Tetramethyl-5-(1-phenylindol-6-yl)-7,13-dihydro-5H-indolo[1,2-b]acridine (compound) 34) Synthesis >

The 7,7,13,13-tetramethyl-7,13-dihydro-5H-indolo[1,2-b]acridine synthesized in Example 1 10.0 g, 9.3 g of 6-bromo-1-phenylindole, 3.6 g of sodium butoxide, and 100 ml of xylene were placed in a reaction vessel substituted with nitrogen, and nitrogen gas was introduced for 1 hour. 0.5 g of ginsyl (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution (50%, w/v) of tri-tert-butylphosphine were added and heated, and stirred at 115 ° C for 6 hours. After cooling to room temperature and adding 100 ml of water, extraction with toluene was carried out, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (support: silica gel, solvent: toluene / n-hexane) to obtain 7,7,13,13-tetramethyl-5-(1-phenylindole-6-yl) A white powder of -7,13-dihydro-5H-indolo[1,2-b]acridine (Compound 34), 10.4 g (yield: 65%).

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 32 hydrogen signals were detected in ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.25(1H), 8.19(1H), 7.90(1H), 7.60-7.80(5H), 7.35-7.60(4H), 7.15-7.30(3H), 7.12(1H), 6.86(2H) , 6.51 (1H), 6.25 (1H), 1.76 (6H), 1.18 (6H).

[Embodiment 8]

For the compound of the present invention, a melting point and a glass transition point were determined by a high-sensitivity differential scanning calorimeter (manufactured by Bruker‧AXS, DSC3100SA).

The compound of the present invention has a glass transition point of 100 ° C or higher, indicating that the compound of the present invention is stable in the state of the film.

[Embodiment 9]

Using the compound of the present invention, 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).

As described above, the compound of the present invention exhibits an ideal energy level as compared with a general hole transporting material such as NPD or TPD, and exhibits an excellent energy transmission ability.

[Embodiment 10]

As shown in FIG. 8, the organic EL device is formed by sequentially depositing a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, and an electron on a glass substrate 1 in which an ITO electrode as a transparent anode 2 is formed in advance. The transport layer 6, the electron injection layer 7, and the cathode (aluminum electrode) 8 are produced.

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 an oxygen plasma treatment. Thereafter, the glass substrate with the ITO electrode attached thereto was mounted in a vacuum vapor deposition machine, and the pressure was reduced to 0.001 Pa or less. Then, HIM-1 of the following structural formula was formed to have a film thickness of 20 nm so as to cover the transparent anode 2, and was used as the hole injection layer 3. On the hole injection layer 3, the compound (Compound 2) of Inventive Example 1 was formed to have a film thickness of 40 nm as the hole transport layer 4. On the hole transport layer 4, the EMD-1 of the following structural formula is binary with the EMH-1 of the following structural formula at an evaporation rate ratio of EMD-1:EMH-1=5:95. The film was deposited to a thickness of 30 nm to form a light-emitting layer 5. On the light-emitting layer 5, Alq _{3 was} formed to have a film thickness of 30 nm as the electron transport layer 6. On the electron transport layer 6, a film of lithium fluoride was formed to have a film thickness of 0.5 nm as the electron injection layer 7. Finally, aluminum was evaporated to a film thickness of 150 nm to form a cathode 8. The characteristics of the organic EL device produced were measured at room temperature in the atmosphere.

The measurement results of the luminescence characteristics when a DC voltage was applied to the organic EL device produced by using the compound (Compound 2) of Example 1 of the present invention are summarized in Table 1.

[Embodiment 11]

The compound of the first embodiment of the present invention which is the material of the hole transport layer 4 in Example 10 The compound 2) was replaced with the compound (Compound 19) of Example 2 of the present invention, and an organic EL device was produced under the same conditions except that the film was formed to have a film thickness of 40 nm. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Embodiment 12]

The compound (Compound 2) of the present invention as the material of the hole transport layer 4 in Example 10 was replaced with the compound (Compound 30) of Example 3 of the present invention, and a film was formed to have a film thickness of 40 nm. An organic EL device was produced under the same conditions except for the above. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Example 13]

The compound (Compound 2) of the present invention as the material of the hole transport layer 4 in Example 10 was replaced with the compound (Compound 31) of Example 4 of the present invention, and a film was formed to have a film thickness of 40 nm. An organic EL device was produced under the same conditions except for the above. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Embodiment 14]

The compound (Compound 2) of the present invention as the material of the hole transport layer 4 in Example 10 was replaced with the compound (Compound 32) of Example 5 of the present invention, and a film was formed to have a film thickness of 40 nm. An organic EL device was produced under the same conditions except for the above. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Example 15]

The compound of the present invention (Compound 2) which is the material of the hole transport layer 4 in Example 10 was replaced with the compound of Example 6 (Compound 33), and the film was formed to have a film thickness of 40 nm. Other than this, an organic EL device was produced under the same conditions. For the organic EL device produced, In the atmosphere, the characteristics are measured at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Example 16]

The compound (Compound 2) of the present invention as the material of the hole transport layer 4 in Example 10 was replaced with the compound (Compound 34) of Example 7 of the present invention, and a film was formed to have a film thickness of 40 nm. An organic EL device was produced under the same conditions except for the above. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

[Comparative Example 1]

For comparison, the compound (Compound 2) of the present invention as the material of the hole transport layer 4 in Example 10 was replaced with HTM-1 of the following structural formula, and the film was formed to have a film thickness of 40 nm. An organic EL device was fabricated under the same conditions. The organic EL device produced was subjected to characteristic measurement at room temperature in the atmosphere. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were summarized in Table 1.

【Table 1】

As shown in Table 1, the organic EL device using HTM-1 was 5.17 V for the driving voltage at a current of a current density of 10 mA/cm ² , whereas the compounds of Examples 1 to 7 of the present invention were used. The organic EL elements are 4.75 to 4.94 V, and both can be driven at a lower voltage. In addition, the organic EL device using HTM-1 is 5.49 lm/W, and the organic EL device using the compounds of Examples 1 to 7 of the present invention is 6.30 to 7.18 lm/W, which is greatly improved. . Further, the organic EL device using the compound of the present invention in terms of luminance and luminous efficiency is improved relative to the organic EL device using HTM-1.

From the above results, it is understood that the organic EL device using the compound having an indole acridine ring-ring structure of the present invention can achieve an improvement in power efficiency or practicality as compared with the organic EL device using the known HTM-1. The drive voltage is reduced.

[Industry Utilization]

The compound having an indole acridine ring-ring structure of the present invention is excellent as a compound for an organic EL device because of its high hole transporting ability, excellent amorphousness, and stable film state. 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 in household electrical products or lighting.

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

Claims (15)

a compound having an indolo-acrididine ring-filled structure represented by the following formula (1); (wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, or a single bond, and B represents A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a vinyl group which may have a substituent, selected from aromatic a disubstituted amino group substituted with a group in a hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group; R ₁ to R ₁₀ may be the same or different and are a hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom or a cyanogen. a base, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom which may have a substituent 5 to 10 cycloalkyloxy, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic rings a condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other by a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom. The bond forms a ring; R ₁₁ to R ₁₄ may be the same or different, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom having 5 substituents. a cycloalkyl group of 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched carbon group having 1 to 6 carbon atoms which may have a substituent. An alkoxy group, a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted, which may have a substituent a condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur with R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ The atoms are bonded to each other to form a ring; here, A is a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a taken Or an unsubstituted condensed polycyclic aromatic divalent group, and B is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group a group, or a vinyl group which may have a substituent, a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, or A and B A single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom is bonded to each other to form a ring). A compound having an indolo-acridin ring-ring structure as claimed in claim 1 is represented by the following formula (1-1); (wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ and Ar ₂ may be used. The same or different, which means a vinyl group which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. , Ar ₁ and Ar ₂ may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring; R ₁ to R ₁₀ may be the same or different and are a hydrogen atom or a ruthenium. An atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom number of 5 to 10 which may have a substituent. a cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent. a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, substituted or a substituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be a single bond, a substituted or unsubstituted methylene group, or an oxygen group. The atom or the sulfur atom is bonded to each other to form a ring; R ₁₁ to R ₁₄ may be the same or different, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and may have a substituent. a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear chain having 1 to 6 carbon atoms which may have a substituent Alkoxy group or branched, a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted group a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, or a methylene group in which R ₁₁ and R ₁₂ , R ₁₃ and R _{14 are each a} single bond, substituted or unsubstituted , an oxygen atom or a sulfur atom is bonded to each other to form a ring; here, A and Ar ₁ may be separated by a single bond, a substituted or unsubstituted methylene group, or an oxygen atom. Or sulfur atoms are bonded to each other to form a ring). A compound having an indolo-acridin ring-ring structure according to the first aspect of the invention, wherein, in the formula (1), A is a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted condensed polycyclic ring. Aromatic 2-valent base. A compound having an indole acridine ring-ring structure according to item 3 of the patent application, wherein in the formula (1), A is a divalent product obtained by removing two hydrogen atoms from a substituted or unsubstituted benzene. base. A compound having an indole acridine ring-filled structure according to item 3 of the patent application, wherein in the formula (1), A is obtained by removing two hydrogen atoms from a substituted or unsubstituted biphenyl. Price base. A compound having an indole acridine ring-filled structure according to the first aspect of the patent application, wherein in the formula (1), A is obtained by taking two hydrogen atoms from a substituted or unsubstituted oxime. Price base. A compound having an indolo-acridin ring-ring structure according to the first aspect of the invention, wherein, in the formula (1), B is a substituted or unsubstituted carbazolyl group. A compound having an indolo-acridin ring-ring structure according to the first aspect of the invention, wherein, in the formula (1), B is a substituted or unsubstituted dibenzofuranyl group. A compound having an indolo-acridin ring-ring structure according to the first aspect of the invention, wherein, in the formula (1), B is a substituted or unsubstituted phenyl group. A compound having an indolo-acridin ring-ring structure according to the first aspect of the invention, wherein, in the formula (1), B is a substituted or unsubstituted biphenyl group. An organic electroluminescent device having a pair of electrodes and at least one organic layer sandwiched therebetween, characterized in that the one having an indole acridine ring structure according to any one of claims 1 to 10 The compound is used as a constituent material of at least one organic layer. The organic electroluminescent device of claim 11, wherein the organic layer is a hole transport layer. The organic electroluminescent device of claim 11, wherein the organic layer is an electron blocking layer. The organic electroluminescence device of claim 11, wherein the organic layer is a hole injection layer. The organic electroluminescent device of claim 11, wherein the organic layer is a light-emitting layer.