KR102232993B1 - Organic electroluminescence element - Google Patents

Abstract

[화학식(1)에 있어서, n은 1∼4의 정수이고, B는 하기 화학식(2)로 표시되는 구조이고, A는 하기 화학식(4)로 표시되는 아민 부위이다.]
[화학식(2)]

[화학식(4)]

A compound having a benzofluorene structure represented by the following formula (1), further comprising an amine compound having a dibenzofuran structure and/or a dibenzothiophene structure, and at least a light emitting layer between the cathode and the anode, or In an organic electroluminescent device in which a plurality of organic thin film layers are sandwiched, at least one layer of the organic thin film layer is an organic electroluminescent device containing the amine compound alone or as a component of a mixture, and is an organic electroluminescent device having a long life and high efficiency. It provides a light emitting device.
[Formula (1)]

[In formula (1), n is an integer of 1 to 4, B is a structure represented by the following formula (2), and A is an amine moiety represented by the following formula (4).]
[Chemical Formula (2)]

[Chemical Formula (4)]

Description

Organic electroluminescent device {ORGANIC ELECTROLUMINESCENCE ELEMENT}

The present invention relates to an organic electroluminescent device. In particular, it relates to an organic electroluminescent device using an aromatic amine derivative having a benzofluorene skeleton.

In general, an organic electroluminescent (EL) device is composed of an anode, a cathode, and one or more organic thin film layers sandwiched between the anode and the cathode. When a voltage is applied between both electrodes, electrons from the cathode side and holes from the anode side are injected into the light emitting region, and the injected electrons and holes recombine in the light emitting region to create an excited state, and the excited state returns to the ground state. Emits light when going.

In addition, since the organic EL device can obtain various luminous colors by using various luminescent materials for the luminescent layer, research on practical use in displays or the like is in full swing. In particular, research on light-emitting materials of three primary colors of red, green, and blue is the most active, and intensive research is being conducted with the aim of improving characteristics.

One of the greatest problems in an organic EL device is to achieve both high luminous efficiency and low driving voltage. As a means of obtaining a highly efficient light emitting device, a method of forming a light emitting layer by doping a host material with a dopant material by several% is known. The host material is required to have high carrier mobility, uniform film formation, and the like, and the dopant material is required to have high fluorescence quantum yield and uniform dispersibility.

As such a material for a light-emitting layer, a benzofluorene compound is described in Patent Documents 1 to 5.

International Publication No. 2007/148660 Pamphlet International Publication No. 2008/062636 Pamphlet US Patent Publication No. 2007-0215889 Japanese Patent Laid-Open No. 2005-290000 International Publication No. 2011/021520 Pamphlet

However, the inventors of the present application found that even when the benzofluorene disclosed in Patent Documents 1 to 5 was used, it could not be said that the improvement was sufficient with respect to the longer life, and that further improvement was required.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an organic EL device having a long life and high efficiency.

The present inventors, as a result of repeated intensive research in order to achieve the above object, further use an amine compound having a dibenzofuran structure and/or a dibenzothiophene structure as a compound having a benzofluorene structure. I found something that can be solved.

That is, the present invention provides the following invention.

[1] An amine compound represented by the following formula (1).

[Formula (1)]

[In formula (1), n is an integer of 1 to 4, B is a structure represented by the following formula (2), and A is an amine moiety represented by the following formula (4).

When n is 2 or more, each A may be the same or different.

[Chemical Formula (2)]

In the formula (2), in the group of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , at least One set represents a bond hand to a divalent group represented by the following formula (3),

R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted cyclic carbon number of 6 to 50 An arylsilyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

[Chemical Formula (3)]

In the formula (3), * represents a bonding site with a group representing a bond hand to a divalent group represented by formula (3) in the formula (2).

In formulas (2) and (3), ^{n of R 1} to ^{R 8} and R ¹¹ to ^{R 14} represents a bond with A,

Of R ¹ to ^{R 8} and R ¹¹ to ^{R 14} , except for the above, each independently a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted ring A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms Group, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or It represents an unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

[Chemical Formula (4)]

In the formula (4), Ar ¹ represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring carbon atoms,

L ¹ and L ² each independently represent a single bond, an arylene group having 6 to 30 ring carbon atoms, a heteroarylene group having 5 to 30 ring atoms, or a divalent linking group formed by bonding 2 to 4 of them,

Any one of R ²¹ to ^{R 28 represents a bond with L 2} , and the others are each independently a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms. Alkylthio group, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or R ²¹ and R ²² , R ²² and R ²³ , R ²³ and At ^{least one combination selected from R 24} , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , and R ²⁷ and R ²⁸ may be bonded to each other to form a saturated or unsaturated ring structure,

X represents an oxygen atom or a sulfur atom,

** represents the binding site to B.]

[2] In the above formula (1), the amine compound according to [1], wherein B is represented by any one of the following formulas (11) to (13).

[Chemical Formulas (11)-(13)]

[In formulas (11) to (13), R ¹ to ^{R 14} are the same as those in formulas (2) and (3), respectively.]

[3] In the formula (2), in the group of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , The amine compound according to [1] or [2], wherein the two groups represent a bond hand to the divalent group represented by the above formula (3).

[4] In the formula (1), the amine compound according to any one of [1] to [3], wherein B is represented by any one of the following formulas (14) to (19).

[Chemical Formulas (14) to (19)]

[In formulas (14) to (19), R ¹ to ^{R 14} are the same as those in the formulas (2) and (3), ^{respectively, and R 11' to R 14'} are each of R ¹¹ to ^{R 14} Same as.]

[5] In the formula (1), the amine compound according to [4], wherein B is represented by the formulas (14) to (16).

[6] The amine compound according to any one of [1] to [5] in the formula (1), wherein X is an oxygen atom.

[7] In the formula (4), the amine compound according to any one of [1] to [6] ^{, wherein L 1 is a single bond.}

[8] The amine compound according to any one of [1] to [7] in the formula (4), wherein L ^{2 is a single bond.}

[9] The amine compound according to any one of [1] to [8] in the formula (4), wherein R ²⁴ or R ²⁵ represents a bond with L ^2.

[10] In the formula (1), the amine compound according to any one of [1] to [9], wherein n is 1 or 2.

^{[11] The amine compound according to any one of [1] to [10], wherein Ar 1} in the formula (4) is a substituted or unsubstituted phenyl group, naphthyl group, or biphenylyl group.

[12] An organic electroluminescent device in which at least one layer including a light emitting layer or an organic thin film layer including a plurality of layers is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer is selected from [1] to [11]. An organic electroluminescent device containing the amine compound according to any one of the components alone or as a component of a mixture.

[13] The organic electroluminescent device according to [12], wherein the light-emitting layer contains the amine compound.

[14] The organic electroluminescent device according to [12] or [13], wherein the at least one layer contains the amine compound according to any one of [1] to [11] and an anthracene derivative represented by the following formula (5). .

[Chemical Formula (5)]

(In the formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, , R ¹⁰¹ to ^{R 108} are each independently a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, a monocyclic group and a condensed cyclic group A group consisting of a combination, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted It is a group selected from an aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted silyl group, a halogen atom, and a cyano group.)

[15] The organic electroluminescent device according to [14], in the formula (5), wherein Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted condensed cyclic group having 8 to 50 ring carbon atoms.

[16] In the formula (5), one of Ar ¹¹ and Ar ¹² is a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, and the other is a substituted or unsubstituted monocyclic group having 8 to The organic electroluminescent device according to [14], which is a 50 condensed cyclic group.

[17] In the formula (5), Ar ¹² is a naphthyl group, a phenanthryl group, a benzanthryl group, or a dibenzofuranyl group, and Ar ¹¹ is an unsubstituted or monocyclic or fused cyclic group substituted phenyl group. The organic electroluminescent device according to [14].

[18] The organic electroluminescent device according to [14], in the formula (5), wherein Ar ¹² is a substituted or unsubstituted condensed cyclic group having 8 to 50 ring atoms, and Ar ^{11 is an unsubstituted phenyl group.}

[19] The organic electroluminescent device according to [14], in the formula (5), wherein Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms.

[20] The organic electroluminescent device according to [1], in the formula (5), wherein Ar ¹¹ and Ar ^{12 are each independently a substituted or unsubstituted phenyl group.}

[21] The organic electroluminescent device according to [14], in the formula (5), wherein Ar ¹¹ is an unsubstituted phenyl group, and Ar ¹² is a phenyl group having a monocyclic group or a condensed cyclic group as a substituent.

[22] The organic electroluminescent device according to [14], in the formula (5), wherein Ar ¹¹ and Ar ¹² are each independently a phenyl group having a monocyclic group or a condensed cyclic group as a substituent.

The organic EL device of the present invention has a long life and high efficiency.

1 is a diagram showing a schematic configuration of an example of an organic electroluminescent device (hereinafter, sometimes abbreviated as "organic EL device") according to an embodiment of the present invention.

In the present invention, "carbon number a to b" in the expression "a substituted or unsubstituted X group having a to b carbon atoms" represents the number of carbon atoms in the case where the X group is unsubstituted, and when the X group is substituted. The number of carbon atoms of the substituent of is not included.

In addition, the "hydrogen atom" includes isotopes with different neutron numbers, that is, protium, deuterium, and tritium.

In addition, an arbitrary substituent in the case of "substituted or unsubstituted" is an alkyl group having 1 to 50 carbon atoms (preferably 1 to 10, more preferably 1 to 5); A cycloalkyl group having 3 to 50 ring carbon atoms (preferably 3 to 6, more preferably 5 or 6); An aryl group having 6 to 50 ring carbon atoms (preferably 6 to 24, more preferably 6 to 12); An aralkyl group having 1 to 50 (preferably 1 to 10, more preferably 1 to 5) carbon atoms having an aryl group having 6 to 50 (preferably 6 to 24, more preferably 6 to 12) ring carbon atoms; Amino group; A mono or dialkylamino group having an alkyl group having 1 to 50 carbon atoms (preferably 1 to 10, more preferably 1 to 5); A mono or diarylamino group having an aryl group having 6 to 50 (preferably 6 to 24, more preferably 6 to 12) ring carbon atoms; An alkoxy group having an alkyl group having 1 to 50 carbon atoms (preferably 1 to 10, more preferably 1 to 5); An aryloxy group having an aryl group having 6 to 50 (preferably 6 to 24, more preferably 6 to 12) ring carbon atoms; Selected from an alkyl group having 1 to 50 carbon atoms (preferably 1 to 10, more preferably 1 to 5) and an aryl group having 6 to 50 ring carbon atoms (preferably 6 to 24, more preferably 6 to 12) Mono-, di- or tri-substituted silyl group having a group to be; The number of ring atoms is 5 to 50 (preferably 5 to 24, more preferably 5 to 12), and 1 to 5 hetero atoms (nitrogen atom, oxygen atom, sulfur atom) (preferably 1 to 3, more Preferably 1 to 2) containing heteroaryl group; A haloalkyl group having 1 to 50 carbon atoms (preferably 1 to 10, more preferably 1 to 5); Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom); Cyano group; It is preferably selected from the group consisting of nitro groups.

Among the above substituents, it is particularly preferable to be selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and an aryl group having 6 to 12 ring carbon atoms.

The amine compound of the present invention is represented by the following formula (1).

[Formula (1)]

[In formula (1), n is an integer of 1 to 4, B is a structure represented by the following formula (2), and A is an amine moiety represented by the following formula (4).

When n is 2 or more, each A may be the same or different.

[Chemical Formula (2)]

In formula (2), at least one of the groups of ^{R 1} and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ^{8 is} Represents a bond hand to a divalent group represented by formula (3),

R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted cyclic carbon number of 6 to 50 An arylsilyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. R ⁹ and R ¹⁰ are each independently preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a phenyl group, a trimethylsilyl group, a triethylsilyl group, or a triphenylsilyl group.

[Chemical Formula (3)]

In the formula (3), * represents a bonding site with a group representing a bond hand to a divalent group represented by formula (3) in the formula (2).

In formulas (2) and (3), ^{n of R 1} to ^{R 8} and R ¹¹ to ^{R 14} represents a bond with A,

Of R ¹ to ^{R 8} and R ¹¹ to ^{R 14} , except for the above, each independently a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted ring A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms Group, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or It represents an unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

In the above formula (1), B is preferably represented by any one of the following formulas (11) to (19).

[Chemical Formulas (11) to (19)]

[In the formulas (11) to (19), R ¹ to ^{R 14} are the same as those in the formulas (2) and (3), ^{respectively, and R 11' to R 14'} are each of the R ¹¹ to ^{R 14} Same as.]

B represented by the formulas (11) to (19) is preferably represented by the following formulas (20) to (46).

[Chemical Formulas (20) to (30)]

[Chemical Formulas (31)-(39)]

[Chemical Formulas (40)-(46)]

[In the formulas (20) to (46), R ^{1 to R 14} and R ^{11' to R 14'} are the same as those in the formulas (11) to (19), and * represents a bond with A, respectively. ]

[Chemical Formula (4)]

[In formula (4), Ar ¹ represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring carbon atoms,

L ¹ and L ² each independently represent a single bond, an arylene group having 6 to 30 ring carbon atoms, a heteroarylene group having 5 to 30 ring atoms, or a divalent linking group formed by bonding 2 to 4 of them,

Any one of R ²¹ to ^{R 28 represents a bond with L 2} , and the others are each independently a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms. Alkylthio group, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or R ²¹ and R ²² , R ²² and R ²³ , R ²³ and At ^{least one combination selected from R 24} , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , and R ²⁷ and R ²⁸ may be bonded to each other to form a saturated or unsaturated ring structure,

X represents an oxygen atom or a sulfur atom,

** represents the binding site to B.]

As the amine moiety represented by the above formula (4), it is preferable that it is represented by the following formula (4-1) or (4-2).

[Chemical Formula (4-1)]

[Chemical Formula (4-2)]

In the formulas (4-1) and (4-2), all of R ²¹ to ^{R 28} , Ar ¹ , L ¹ and L ² are the same as those in the formula (4).

As the amine compound of the present invention represented by the above formula (1), A is represented by the above formula (4-1) or (4-2), and B is one of the above formulas (20) to (45). It is preferable that it is displayed, and it is particularly preferable that n is 2.

In the above formula (1), n is preferably 1 or 2, and more preferably 2.

In the formula (4), X is preferably an oxygen atom, and R ²² , R ²⁴ , R ²⁵ or R ²⁷ is preferably a bond with L ^{2 , and R 24} or R ²⁵ is a bond with ^{L 2.} It is more preferable. When R ²⁴ or R ²⁵ is ^{a bond with L 2} , light emission at a shorter wavelength is obtained, and when these materials are used, an organic EL device that emits light with high blue purity can be obtained.

Examples of the alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. , s-butyl group, t-butyl group, pentyl group (including isomers), hexyl group (including isomers), heptyl group (including isomers), octyl group (including isomers), nonyl group ( Isomers), decyl group (including isomers), undecyl group (including isomers), and dodecyl group (including isomers), and the like, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and pentyl group (including isomers) are preferable, and methyl group, ethyl group, n-propyl group, isopropyl group, n-view A yl group, an isobutyl group, an s-butyl group, and a t-butyl group are more preferable, and a methyl group, an ethyl group, an isopropyl group and a t-butyl group are particularly preferable.

Examples of the cycloalkyl group having 3 to 20 ring carbon atoms (preferably 3 to 6, more preferably 5 or 6) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooxy group. And a tyl group and an adamantyl group, and a cyclopentyl group and a cyclohexyl group are preferable.

Examples of the alkylsilyl group having 3 to 50 carbon atoms include a monoalkylsilyl group, a dialkylsilyl group, and a trialkylsilyl group, and specific examples of each alkyl group are the same as the above-described alkylsilyl group.

Examples of the arylsilyl group having 6 to 50 ring carbon atoms include a monoarylsilyl group, a diarylsilyl group, and a triarylsilyl group, and specific examples of each aryl group are the same as the aryl groups described later.

As a specific example of the said C1-C20 alkoxy group, it is the same as the above-mentioned alkyl group.

As a specific example of the said ring-forming C6-C30 aryloxy group, it is the same as the aryl group mentioned later.

As a specific example of the said C1-C20 alkylthio group, it is the same as the above-mentioned alkyl group.

As a specific example of the C6-C30 arylthio group, it is the same as the aryl group mentioned later.

Examples of the aryl group having 6 to 30 ring carbon atoms (preferably 6 to 24 ring carbon atoms, more preferably 6 to 18 ring carbon atoms) include, for example, phenyl group, naphthylphenyl group, biphenylyl group, terphenylyl group, Naphthyl group, acenaphthylene group, anthryl group, benzanthryl group, aseanthryl group, phenanthryl group, benzo[c]phenanthryl group, phenalenyl group, fluorenyl group, picenyl group, pentaphenyl group, pyrenyl group, Chrysenyl group, benzo[g]chrysenyl group, s-indasenyl group, as-indasenyl group, fluoranthenyl group, benzo[k]fluoranthenyl group, triphenylenyl group, benzo[b]triphenylene Diary and peryleneyl group, etc. are mentioned, A phenyl group, a biphenylyl group, a terphenylyl group, and a naphthyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is especially preferable.

Examples of the aryl group having a substituent include a phenylnaphthyl group, a naphthylphenyl group, a tolyl group, a xylyl group, a 9,9-dimethylfluorenyl group, and a 9,9-diphenylfluorenyl group.

A heteroaryl group having 5 to 30 ring atoms (preferably 6 to 24 ring atoms, more preferably 6 to 18 ring atoms) heteroaryl groups is at least 1, preferably 1 to 5 heteroatoms, such as , Nitrogen atom, sulfur atom and oxygen atom. Examples of the heteroaryl group include pyrrolyl group, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, oxazolyl group, thiazolyl group, Pyrazolyl group, isoxazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolel group, benzofuranyl group, isobenzofuran Diary, benzothiophenyl group, isobenzothiophenyl group, indolizinyl group, quinolizinyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimi Dazolyl group, benzoxazolyl group, benzothiazolyl group, indazolyl group, benzisooxazolyl group, benzisothiazolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, phenanthridine Diary, acridinyl group, phenanthrolinyl group, phenazineyl group, phenothiazinyl group, phenoxazineyl group, and xantenyl group, and the like, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidine Diary, pyrazinyl group, triazinyl group, benzofuranyl group, benzothiophenyl group, dibenzofuranyl group, dibenzothiophenyl group are preferable, and benzofuranyl group, benzothiophenyl group, dibenzofuranyl group, dibenzothiophene Diary is more preferable.

Specific examples of the amine compound represented by the formula (1) are shown below, but are not limited to the following compounds.

The amine compound is useful as a material for an organic EL device, particularly as a dopant material for a fluorescent light emitting layer. The method for preparing the amine compound is not particularly limited, and those skilled in the art can easily prepare it by using and changing a known synthetic reaction while referring to the examples of the present specification.

(Organic EL element)

Next, the organic EL device of the present invention will be described.

The organic EL device of the present invention is characterized in that it has an organic thin film layer containing a light emitting layer between a cathode and an anode, and at least one of the organic thin film layers contains the aforementioned amine compound.

Examples of the organic thin film layer containing the above-described amine compound include, but are not limited to, a hole transport layer, a light emitting layer, a space layer, and a barrier layer. The above-described amine compound is preferably included in the light emitting layer, particularly preferably included as a dopant material for the fluorescent light emitting layer, and a long lifespan of the organic EL device can be expected.

The organic EL device of the present invention may be a fluorescent or phosphorescent monochromatic light emitting device, a fluorescent/phosphorescent hybrid white light emitting device, a simple type having a single light emitting unit, or a tandem type having a plurality of light emitting units. . Here, the "light-emitting unit" refers to a minimum unit capable of emitting light by recombination of one or more organic layers, one of which is a light-emitting layer, and recombination of injected holes and electrons.

Therefore, as a typical device configuration of a simple organic EL device, the following device configuration is exemplified.

(1) anode/light-emitting unit/cathode

In addition, the light-emitting unit may be a stacked type having a plurality of phosphorescent layers or fluorescent light-emitting layers, and in that case, a space layer may be provided between each light-emitting layer for the purpose of preventing excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer. do. A typical layer structure of the light emitting unit is shown below.

(a) hole transport layer/light-emitting layer (/electron transport layer)

(b) hole transport layer/first fluorescent light-emitting layer/second fluorescent light-emitting layer (/electron transport layer)

(c) hole transport layer/phosphorescent layer/space layer/fluorescent light emitting layer (/electron transport layer)

(d) hole transport layer/first phosphorescent layer/second phosphorescent layer/space layer/fluorescent light emitting layer (/electron transport layer)

(e) hole transport layer/first phosphorescent light emitting layer/space layer/second phosphorescent light emitting layer/space layer/fluorescent light emitting layer (/electron transport layer)

(f) hole transport layer/phosphorescent layer/space layer/first fluorescent light emitting layer/second fluorescent light emitting layer (/electron transport layer)

Each of the phosphorescent or fluorescent light emitting layers may each exhibit different luminous colors. Specifically, in the stacked light emitting layer (d), the same layer structure as the hole transport layer/first phosphorescent light emitting layer (red light emission)/second phosphorescent light emitting layer (green light emission)/space layer/fluorescent light emitting layer (blue light emission)/electron transport layer Can be mentioned.

On the other hand, an electron barrier layer may be appropriately provided between each light emitting layer and the hole transport layer or the space layer. Moreover, you may provide a hole barrier layer suitably between each light emitting layer and an electron transport layer. By providing an electron barrier layer or a hole barrier layer, electrons or holes are confined in the light emitting layer, the probability of recombination of charges in the light emitting layer is increased, and light emission efficiency can be improved.

As a typical device configuration of a tandem type organic EL device, the following device configurations are exemplified.

(2) anode/first light-emitting unit/intermediate layer/second light-emitting unit/cathode

Here, as the first light-emitting unit and the second light-emitting unit, for example, each independently selected from the same light-emitting unit as the above-described light-emitting unit.

The intermediate layer is generally also referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extracting layer, a connection layer, and an intermediate insulating layer, and supplies electrons to the first light-emitting unit and holes to the second light-emitting unit, Known material configurations can be used.

Fig. 1 shows a schematic configuration of an example of the organic EL device of the present invention. The organic EL element 1 has a substrate 2, an anode 3, a cathode 4, and a light-emitting unit 10 disposed between the anode 3 and the cathode 4. The light-emitting unit 10 has a light-emitting layer 5 comprising at least one fluorescent light-emitting layer containing a fluorescent host material and a fluorescent dopant. A hole transport layer 6 or the like may be formed between the light emitting layer 5 and the anode 3, and an electron transport layer 7 or the like may be formed between the light emitting layer 5 and the cathode 4. Further, an electron barrier layer may be provided on the anode 3 side of the light-emitting layer 5 and a hole barrier layer may be provided on the cathode 4 side of the light-emitting layer 5, respectively. Thereby, electrons and holes are confined in the light-emitting layer 5, and the probability of generating excitons in the light-emitting layer 5 can be increased.

Meanwhile, in the present specification, a host combined with a fluorescent dopant is referred to as a fluorescent host, and a host combined with a phosphorescent dopant is referred to as a phosphorescent host. The fluorescent host and the phosphorescent host are not only distinguished by their molecular structure. That is, a fluorescent host means a material constituting a fluorescent light-emitting layer containing a fluorescent dopant, and does not mean that it cannot be used as a material constituting a phosphorescent light-emitting layer. The same is true for the phosphorescent host.

(Board)

The organic EL device of the present invention is fabricated on a translucent substrate. The light-transmitting substrate is a substrate that supports the organic EL element, and a substrate having a transmittance of 50% or more of light in the visible region of 400 nm to 700 nm is preferable. Specifically, a glass plate, a polymer plate, etc. are mentioned. As the glass plate, in particular, soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like are used as raw materials. Further, examples of the polymer plate include those made of polycarbonate, acrylic, polyethylene terephthalate, polyethersulfide, polysulfone, and the like as raw materials.

(anode)

The anode of the organic EL device is responsible for injecting holes into the hole transport layer or the light emitting layer, and it is effective to use a material having a work function of 4.5 eV or more. Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like. The anode can be produced by forming a thin film of these electrode materials by a method such as a vapor deposition method or a sputtering method. When light emission from the light-emitting layer is extracted from the anode, it is preferable that the transmittance of light in the visible region of the thin film is greater than 10%. In addition, the sheet resistance is preferably several hundred Ω/□ or less. Moreover, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 µm, preferably 10 nm to 200 nm. When the light transmittance, sheet resistance, and film thickness of the thin film are within the above ranges, an increase in driving voltage and a decrease in luminance are suppressed, which is preferable.

(cathode)

The cathode serves to inject electrons into the electron injection layer, the electron transport layer, or the light-emitting layer, and is preferably formed of a material having a small work function. The negative electrode material is not particularly limited, but specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy, and the like may be used. Like the anode, the cathode can also be produced by forming a thin film by a method such as a vapor deposition method or a sputtering method. Further, if necessary, light emission may be extracted from the cathode side.

(Luminescent layer)

It is an organic layer having a light emitting function, and when a doping system is employed, it contains a host material and a dopant material. At this time, the host material mainly promotes recombination of electrons and holes, and has a function of confining excitons in the light emitting layer, and the dopant material has a function of efficiently emitting excitons obtained by recombination.

In the case of a phosphorescent device, the host material has a function of confining excitons mainly generated by a dopant in the light emitting layer.

Here, as the light emitting layer, for example, a double host (also referred to as a host cohost) may be employed to adjust the carrier balance in the light emitting layer by combining an electron-transporting host and a hole-transporting host.

Further, by adding two or more types of dopant materials having a high quantum yield, a double dopant in which each dopant emits light may be employed. Specifically, the embodiment of realizing yellow light emission by making the light-emitting layer common by co-depositing a host, a red dopant, and a green dopant is mentioned.

When the light-emitting layer is formed as a laminate in which a plurality of light-emitting layers are stacked, electrons and holes are accumulated at the interface of the light-emitting layer, and the recombination region is concentrated at the interface of the light-emitting layer, thereby improving quantum efficiency.

The easiness of injecting holes into the light-emitting layer and the ease of injecting electrons may be different, and the hole-transporting ability and electron-transporting ability represented by the mobility of holes and electrons in the light-emitting layer may be different.

The light emitting layer can be formed by a known method such as a vapor deposition method, a spin coating method, or an LB method. Further, a light emitting layer can also be formed by thinning a solution obtained by dissolving a binder such as a resin and a material compound in a solvent by spin coating or the like.

It is preferable that the light emitting layer is a molecular deposition film. Molecular deposition film refers to a thin film formed by depositing from a material compound in a gaseous state, or a film formed by solidification from a material compound in a solution or liquid state. Can be distinguished by a cohesive structure, a difference in a higher-order structure, or a functional difference resulting from it.

The thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and still more preferably 10 to 50 nm. If it is 5 nm or more, formation of the light emitting layer is easy, and if it is 50 nm or less, an increase in driving voltage can be avoided.

(Dopant material)

The fluorescent dopant (fluorescent light-emitting material) forming the light-emitting layer is a compound capable of emitting light from a singlet excited state, and is not particularly limited as long as it emits light from a singlet excited state, but the compound of formula (1) of the present invention comprises a light emitting layer. It is preferably used as a dopant material to be formed. Others, as dopant materials, include fluoranthene derivatives, styrylarylene derivatives, pyrene derivatives, arylacetylene derivatives, fluorene derivatives, boron complexes, perylene derivatives, oxadiazole derivatives, anthracene derivatives, styrylamine derivatives, arylamines Derivatives and the like, preferably anthracene derivatives, fluoranthene derivatives, styrylamine derivatives, arylamine derivatives, styrylarylene derivatives, pyrene derivatives, boron complexes, more preferably anthracene derivatives, fluoranthene derivatives , Styrylamine derivatives, arylamine derivatives, and boron complex compounds.

The content of the fluorescent dopant in the light emitting layer is not particularly limited and can be appropriately selected according to the purpose, but, for example, 0.1 to 70 mass% is preferable, 1 to 30 mass% is more preferable, and 1 to 20 mass% is more preferable. And 1 to 10% by mass is even more preferable. When the content of the fluorescent dopant is 0.1% by mass or more, sufficient light emission is obtained, and when it is 70% by mass or less, concentration quenching can be avoided.

(Host)

Examples of the host of the light emitting layer include an anthracene derivative, a polycyclic aromatic skeleton-containing compound, and the like, preferably an anthracene derivative.

As the host of the blue light emitting layer, for example, an anthracene derivative represented by the following formula (5) can be used.

[Chemical Formula (5)]

(In the formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, , R ¹⁰¹ to ^{R 108} are each independently a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, a monocyclic group and a condensed cyclic group A group consisting of a combination of, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted It is a group selected from a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted silyl group, a halogen atom, and a cyano group.)

The monocyclic group in the general formula (5) is a group composed only of a ring structure that does not have a condensed structure.

Specific examples of a monocyclic group having 5 to 50 ring atoms (preferably 5 to 30 ring atoms, more preferably 5 to 20 ring atoms) include phenyl group, biphenylyl group, terphenylyl group, and quarterphenyl Aromatic groups, such as a reel group, and heterocyclic groups, such as a pyridyl group, a pyrazyl group, a pyrimidyl group, a triazinyl group, a furyl group, and a thienyl group, are preferable.

As the monocyclic group, among them, a phenyl group, a biphenylyl group, and a terphenylyl group are preferable.

The condensed cyclic group in the general formula (5) is a group in which two or more ring structures are fused.

As the condensed cyclic group having 8 to 50 ring atoms (preferably 8 to 30 ring atoms, more preferably 8 to 20 ring atoms), specifically, naphthyl group, phenanthryl group, and anthryl group , Chrysenyl group, benzanthryl group, benzophenanthryl group, triphenylenyl group, benzocrysenyl group, indenyl group, fluorenyl group, 9,9-dimethylfluorenyl group, benzofluorenyl group, dibenzoflu Condensed aromatic ring groups such as orenyl group, fluoranthenyl group, benzofluoranthenyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, quinolyl group And a condensed heterocyclic group such as a phenanthrolinyl group.

As the condensed cyclic group, among others, naphthyl group, phenanthryl group, anthryl group, 9,9-dimethylfluorenyl group, fluoranthenyl group, benzanthryl group, dibenzothiophenyl group, dibenzofuranyl group, Carbazolyl groups are preferred.

On the other hand, ^{the substituent of Ar 11} and Ar ¹² is preferably the monocyclic group or condensed cyclic group described above.

Specific examples of the alkyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, substituted silyl group and halogen atom in formula (5) are R ¹ to in formulas (2) to (3) described above. It is the same as that referred to as ^{R 14 or as an arbitrary substituent.}

Below, only preferable specific examples in formula (5) are given.

The anthracene derivative represented by the formula (5) is preferably any one of the following anthracene derivatives (A), (B) and (C), and is selected according to the configuration of the organic EL device to be applied and the required characteristics.

(Anthracene derivative (A))

The anthracene derivative is composed of a condensed cyclic group having 8 to 50 ring atoms ^{in which Ar 11} and Ar ¹² in the general formula (5) are each independently substituted or unsubstituted. The anthracene derivatives ^{can be divided into cases where Ar 11} and Ar ¹² are the same substituted or unsubstituted condensed cyclic group, and different substituted or unsubstituted condensed cyclic groups.

^{Anthracene derivatives which are substituted or unsubstituted condensed cyclic groups in which Ar 11} and Ar ¹² in the general formula (5) are different (including the difference in the substitution position) are particularly preferable, and preferable specific examples of the condensed ring are as described above. Among them, a naphthyl group, a phenanthryl group, a benzanthryl group, a 9,9-dimethylfluorenyl group, and a dibenzofuranyl group are preferable.

(Anthracene derivative (B))

The anthracene derivative is a monocyclic group having 5 ^{to 50 ring atoms in which one of Ar 11} and Ar ¹² in the general formula (5) is substituted or unsubstituted, and the other is 8 substituted or unsubstituted ring atoms. It is composed of ∼50 condensed cyclic groups.

In a preferred embodiment, Ar ¹² is a naphthyl group, a phenanthryl group, a benzanthryl group, a 9,9-dimethylfluorenyl group, or a dibenzofuranyl group, and Ar ¹¹ is unsubstituted or substituted with a monocyclic or condensed cyclic group. It is a phenyl group.

Specific groups of preferable monocyclic groups and condensed cyclic groups are as described above.

As another preferred embodiment, Ar ¹² is a condensed ^{cyclic group, and Ar 11} is an unsubstituted phenyl group. In this case, as the condensed cyclic group, a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, and a benzanthryl group are particularly preferable.

(Anthracene derivative (C))

In the anthracene derivative, Ar ¹¹ and Ar ¹² in the general formula (5) are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms.

In a preferred embodiment, both of Ar ¹¹ and Ar ¹² are substituted or unsubstituted phenyl groups.

In a more preferred embodiment, Ar ¹¹ is an unsubstituted phenyl group, Ar ¹² is a phenyl group having a monocyclic group or a condensed cyclic group as a substituent, and Ar ¹¹ and Ar ¹² are each independently a phenyl group having a monocyclic group and a condensed cyclic group as a substituent There is a case.

Specific examples of the preferred monocyclic group and condensed cyclic group as the substituent are as described above. More preferably, as a monocyclic group as a substituent, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, and a benzanthryl group are used as the condensed cyclic group.

Specific examples of the anthracene derivative represented by the general formula (5) include those shown below.

(Electron donating dopant)

It is also preferable that the organic EL device of the present invention has an electron donating dopant in the interface region between the cathode and the light emitting unit. According to such a configuration, an improvement in light emission luminance and a longer life in the organic EL device can be achieved. Here, the electron donating dopant refers to a material containing a metal having a work function of 3.8 eV or less, and specific examples thereof include an alkali metal, an alkali metal complex, an alkali metal compound, an alkaline earth metal, an alkaline earth metal complex, and an alkaline earth metal compound. , At least one selected from rare earth metals, rare earth metal complexes, and rare earth metal compounds.

Examples of the alkali metal include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like, and the work function is 2.9 eV. It is particularly preferable that it is the following. Examples of the alkaline earth metal include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), and the like, particularly preferably 2.9 eV or less. . Examples of the rare earth metal include Sc, Y, Ce, Tb, and Yb, and it is particularly preferable that the work function is 2.9 eV or less.

Examples of the alkali metal compound include alkali oxides such as Li ₂ O, Cs ₂ O, and K ₂ O, alkali halides such as LiF, NaF, CsF, and KF, and LiF, Li ₂ O, and NaF are preferable. . Examples of the alkaline earth metal compound include BaO, SrO, CaO, and Ba _x Sr _{1 -x} O (0 <x <1), Ba _x Ca _1-x O (0 <x <1) and the like in which they are mixed, BaO, SrO and CaO are preferred. Examples of the rare earth metal compound include YbF ₃ , ScF ₃ , ScO ₃ , Y ₂ O ₃ , Ce ₂ O ₃ , GdF ₃ and TbF ₃ , and YbF ₃ , ScF ₃ and TbF ₃ are preferable.

The alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as they each contain at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions as metal ions. In addition, as a ligand, quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, and hydride Roxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azometha And humans and their derivatives.

As the form of addition of the electron-donating dopant, it is preferable to form a layer or island in the interface region. As the formation method, a method of dispersing an electron donating dopant in the organic compound by simultaneously evaporating an organic compound (a light emitting material or an electron injecting material) forming an interface region while depositing an electron-donating dopant by a resistance heating evaporation method is preferable. Do. The dispersion concentration is an organic compound: electron donating dopant = 100:1 to 1:100 in a molar ratio.

In the case of forming the electron-donating dopant in a layered form, after forming a light emitting material or an electron injecting material as an organic layer at the interface in a layered form, a reducing dopant alone is vapor-deposited by resistance heating evaporation, and the thickness of the layer is preferably 0.1 nm. It is formed in -15 nm. When the electron-donating dopant is formed in an island shape, after forming a light emitting material or an electron injecting material as an organic layer at the interface into an island shape, an electron-donating dopant alone is deposited by resistance heating evaporation, and the thickness of the island is from 0.05 nm to It is formed at 1 nm.

In the organic EL device of the present invention, the ratio of the main component and the electron-donating dopant is preferably the main component: electron-donating dopant = 5:1 to 1:5 by molar ratio.

(Electron transport layer)

It is an organic layer formed between the emission layer and the cathode, and has a function of transporting electrons from the cathode to the emission layer. When the electron transport layer is composed of a plurality of layers, an organic layer close to the cathode may be defined as an electron injection layer. The electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit.

As the electron-transporting material used for the electron-transporting layer, an aromatic heterocyclic compound containing at least one hetero atom in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable. Further, as the nitrogen-containing ring derivative, an aromatic ring having a nitrogen-containing 6-membered ring or 5-membered ring skeleton, or a condensed aromatic ring compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton is preferable.

As the nitrogen-containing ring derivative, for example, a nitrogen-containing ring metal chelate complex represented by the following general formula (A) is preferable.

[Chemical Formula (A)]

^{R 2} to ^{R 7} in the general formula (A) are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and 6 It is an aryloxy group of to 50, an alkoxycarbonyl group, or an aromatic heterocyclic group having 5 to 50 ring carbon atoms, and these may be substituted.

M is aluminum (Al), gallium (Ga), or indium (In), preferably In.

L is a group represented by the following formula (A') or (A").

[Chemical Formula (A')]

[Chemical Formula (A")]

In formula (A'), R ⁸ to ^{R 12} are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other may form a cyclic structure. In addition, in the formula (A"), R ^{13 to R 27} are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other may form a cyclic structure. .

As the electron-transmitting compound used in the electron-transporting layer, 8-hydroxyquinoline or a metal complex of a derivative thereof, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative is suitable.

As for these electron-transmitting compounds, those having good thin film formation properties are preferably used. And the following are mentioned as a specific example of these electron transporting compounds.

The nitrogen-containing heterocyclic derivative as the electron-transmitting compound is a nitrogen-containing heterocyclic derivative composed of an organic compound having the following general formula (D), and includes a nitrogen-containing compound other than a metal complex.

[Chemical Formula (D)]

It is particularly preferable that the electron transport layer of the organic EL device of the present invention contains at least one nitrogen-containing heterocyclic derivative represented by the following formulas (60) to (62).

[Chemical Formula (60)]

[Chemical Formula (61)]

[Chemical Formula (62)]

(In the formula, Z ¹ , Z ² and Z ³ are each independently a nitrogen atom or a carbon atom.

R ¹ and R ² are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a substituted or unsubstituted C 1 to 20 carbon atom. Is an alkyl group of, a substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

n is an integer of 0 to 5, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different from each other. Further, two adjacent R ^1s may be bonded to each other to form a substituted or unsubstituted hydrocarbon ring.

Ar ¹ is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.

Ar ² is a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 haloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted ring It is an aryl group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.

However, either of Ar ¹ or Ar ² is a substituted or unsubstituted condensed aromatic hydrocarbon ventilation having 10 to 50 ring carbon atoms, or a substituted or unsubstituted condensed aromatic heterocyclic group having 9 to 50 ring atoms.

Ar ³ is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms.

L ¹ , L ² and L ³ are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent condensed aromatic heterocyclic group having 9 to 50 ring atoms to be.)

Specific examples of the nitrogen-containing heterocyclic derivatives represented by the above formulas (60) to (62) include those shown below.

The film thickness of the electron transport layer is not particularly limited, but is preferably 1 nm to 100 nm.

In addition, as a constituent component of the electron injection layer that can be provided adjacent to the electron transport layer, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative. When the electron injection layer is made of an insulator or a semiconductor, leakage of current can be effectively prevented and electron injection properties can be improved.

As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable because electron injection properties can be further improved. Specifically, preferred alkali metal chalcogenides include, for example, Li ₂ O, K ₂ O, Na ₂ S, Na ₂ Se and Na ₂ O, and preferred alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS and CaSe are mentioned. Moreover, as a preferable alkali metal halide, LiF, NaF, KF, LiCl, KCl, NaCl, etc. are mentioned, for example. Also, as the preferred alkaline earth metal halides of, for example, CaF _2, BaF _2, SrF _2, MgF ₂ and BeF _2, there may be mentioned such as a fluoride or halides other than the fluorides.

In addition, as a semiconductor, an oxide, nitride, or oxynitride containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn, etc. One type alone or a combination of two or more may be mentioned. Further, it is preferable that the inorganic compound constituting the electron injection layer is a microcrystalline or amorphous insulating thin film. When the electron injection layer is composed of these insulating thin films, a more homogeneous thin film is formed, and thus pixel defects such as dark spots can be reduced. On the other hand, examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides.

When using such an insulator or semiconductor, the preferred thickness of the layer is about 0.1 nm to 15 nm. In addition, it is preferable that the electron injection layer in the present invention contains the electron-donating dopant described above.

(Hole transport layer)

It is an organic layer formed between the light emitting layer and the anode, and has a function of transporting holes from the anode to the light emitting layer. When the hole transport layer is composed of a plurality of layers, an organic layer close to the anode may be defined as a hole injection layer. The hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit.

As another material for forming the hole transport layer, an aromatic amine compound, such as an aromatic amine derivative represented by the following formula (I), is suitably used.

[Formula (I)]

In the formula (I), Ar ^{1 to} Ar ⁴ are a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms or a condensed aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms. A ventilated or condensed aromatic heterocyclic group, or a group in which these aromatic hydrocarbon groups or condensed aromatic hydrocarbon groups are bonded to an aromatic heterocyclic group or a condensed aromatic heterocyclic group.

You may form a ring with ^{Ar 1} and Ar ² , and Ar ³ and Ar ^4.

In addition, in the formula (I), L is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms or a condensed aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms Or a condensed aromatic heterocyclic group.

Specific examples of the compound of formula (I) are described below.

In addition, aromatic amines of the following formula (II) are also suitably used for formation of the hole transport layer.

[Formula (II)]

In the formula (II), ^{the definition of Ar 1 to} Ar ³ is the same as the definition ^{of Ar 1 to} Ar ⁴ in the formula (I). Specific examples of the compound of formula (II) are described below, but are not limited thereto.

The hole transport layer of the organic EL device of the present invention may have a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).

The film thickness of the hole transport layer is not particularly limited, but it is preferably 10 to 200 nm.

In the organic EL device of the present invention, a layer containing an acceptor material may be bonded to the anode side of the hole transport layer or the first hole transport layer. Accordingly, a reduction in the driving voltage and a reduction in manufacturing cost are expected.

As the acceptor material, a compound represented by the following formula is preferable.

The film thickness of the layer containing the acceptor material is not particularly limited, but it is preferably 5 to 20 nm.

(n/p doping)

In the above-described hole transport layer or electron transport layer, the carrier injection ability can be adjusted by doping (n) of a donor material or doping (p) of an acceptor material, as described in Japanese Patent No. 3695714. have.

As a representative example of n doping, a method of doping an electron transport material with a metal such as Li or Cs is mentioned, and a representative example of p doping is a method of doping a hole transport material with an acceptor material such as _{F 4 TCNQ.} have.

(Space floor)

The space layer is, for example, a layer provided between the fluorescent light-emitting layer and the phosphorescent light-emitting layer for the purpose of not diffusing excitons generated in the phosphorescent light-emitting layer to the fluorescent light-emitting layer or adjusting carrier balance when stacking the fluorescent light-emitting layer and the phosphorescent light-emitting layer. to be. Further, the space layer may be provided between a plurality of phosphorescent light emitting layers.

Since the space layer is provided between the light emitting layers, it is preferable that it is a material having both electron transport and hole transport properties. Further, in order to prevent diffusion of the triplet energy in the adjacent phosphorescent light emitting layer, it is preferable that the triplet energy is 2.6 eV or more. Examples of the material used for the space layer include those similar to those used for the hole transport layer described above.

(Barrier layer)

It is preferable that the organic EL device of the present invention has a barrier layer such as an electron barrier layer, a hole barrier layer, and a triplet barrier layer in a portion adjacent to the light emitting layer. Here, the electron barrier layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer, and the hole barrier layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer.

The triplet barrier layer prevents the diffusion of triplet excitons generated in the light emitting layer into the surrounding layer and confines the triplet excitons in the light emitting layer, as described later, so that molecules of the electron transport layer other than the light emitting dopant of the triplet excitons It has a function of suppressing energy deactivation in the phase.

It is preferable that the ^{electron injection layer is 10 -6} cm ² /Vs or more in the range of the electric field strength of 0.04 to 0.5 MV/cm. This is because the injection of electrons from the cathode into the electron transport layer is promoted, and further injection of electrons into the adjacent barrier layer and the light emitting layer is promoted, thereby enabling driving at a lower voltage.

Example

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

Synthesis Example 1 (Synthesis of Compound 1)

(1-1) Synthesis of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene

To a mixture of 7,7-diphenylbenzo[c]fluorene synthesized with reference to the method described in WO 2007/119800, 85 mL of acetic acid and 85 mL of dichloromethane were added, 23.3 g of benzyl trimethylammonium tribromide was added. Thereafter, zinc chloride was added until all of the benzyl trimethylammonium tribromide was dissolved (30 g), and reacted at room temperature for 8 hours. A 5% aqueous sodium hydrogensulfite solution was added to the reaction mixture, followed by extraction with dichloromethane, the dichloromethane layer was washed with an aqueous potassium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography and recrystallization to obtain 9.72 g (yield 68%) of a white solid of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene.

(1-2) Synthesis of Compound 1

In an argon atmosphere, 2.5 g of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene synthesized in (1-1), 4-( 3.6 g of 4-isopropylphenylamino)dibenzofuran, 0.13 g of trisdibenzylideneacetonedipalladium (0), 0.91 g of sodium-t-butoxide were dissolved in 24 mL of toluene, and 96 mg of tri-t-butylphosphine A solution dissolved in 0.17 mL of toluene was added, followed by stirring at 85°C for 8 hours. The reaction solution was cooled to room temperature, filtered through Celite, and the solvent was distilled off, and the obtained residue was purified by silica gel column chromatography and recrystallization to obtain 1.92 g (yield: 41%) of a yellow solid of Compound 1. As a result of mass spectrum analysis, the obtained compound was compound 1, and it was m/e=966 with respect to molecular weight 966.42.

Synthesis Example 2 (Synthesis of Compound 2)

(2-1) Synthesis of 7-trimethylsilylbenzo[c]fluorene

「Organic Letters, Vol. 11, No. 20, 2009, pages 4588∼4591", synthesized benzo[c]fluorene 22.8g and dehydrated tetrahydrofuran 500mL were added, cooled to -65℃, and then n-butyllithium hexane solution (1.65M) 70 mL was put, and it stirred for 1 hour. Subsequently, after dropping 18 mL of trimethylsilyl chloride, the temperature was gradually raised and stirred at room temperature for 4 hours.

After separation and extraction by adding fresh water and toluene, the organic layer was washed with an aqueous sodium carbonate solution and saturated brine, dried over sodium sulfate, and the crude product obtained by concentration was purified by silica gel chromatography, and the obtained solid was dried under reduced pressure. , 27.3 g of a white solid was obtained.

(2-2) Synthesis of 7,7-bis(trimethylsilyl)benzo[c]fluorene

In the synthesis of 7-trimethylsilylbenzo[c]fluorene, it was synthesized in the same manner using 7-trimethylsilylbenzo[c]fluorene instead of benzo[c]fluorene.

(2-3) Synthesis of 5,9-dibromo-7,7-bis(trimethylsilyl)benzo[c]fluorene

To a mixture of 7,7-bis(trimethylsilyl)benzo[c]fluorene, 42 mL of acetic acid and 42 mL of dichloromethane were added, 11.7 g of benzyltrimethylammonium tribromide was added, and then 15 g of zinc chloride was added to benzyltri. It was added until all methylammonium tribromide was dissolved, and reacted at room temperature for 8 hours.

A 5% aqueous sodium hydrogensulfite solution was added to the reaction mixture, followed by extraction with dichloromethane, the dichloromethane layer was washed with an aqueous potassium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography and recrystallization to obtain 4.2 g (yield 60%) of a white solid of 5,9-dibromo-7,7-bis(trimethylsilyl)benzo[c]fluorene.

(2-4) Synthesis of Compound 2

In step (1-2) of Synthesis Example 1, 5,9-dibromo-7 synthesized in (2-3) instead of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except for using 7-bis(trimethylsilyl)benzo[c]fluorene to obtain compound 2. As a result of mass spectrum analysis, the obtained compound was compound 2, and it was m/e=958 with respect to molecular weight 958.43.

Synthesis Example 3 (Synthesis of Compound 3)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(phenylamino)dibenzofuran synthesized by referring to the method described in WO 2010/122810 Except having used, it produced similarly to the process (1-2) of Synthesis Example 1, and obtained the compound 3. As a result of mass spectrum analysis, the obtained compound was compound 3, and it was m/e=882 with respect to molecular weight 882.31.

Synthesis Example 4 (Synthesis of Compound 4)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(4-trimethylsilylphenyl synthesized by referring to the method described in WO 10/122810) Except for using amino) dibenzofuran, it was prepared in the same manner as in the step (1-2) of Synthesis Example 1 to obtain compound 4. The obtained compound was a compound 4 as a result of mass spectrum analysis, and m/e=1026 with respect to a molecular weight of 1026.40.

Synthesis Example 5 (Synthesis of Compound 5)

In the step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, N,N-bis(dibenzofuran) synthesized by referring to the method described in WO 2010/122810 Except having used -4-yl)amine, it produced similarly to the process (1-2) of Synthesis Example 1, and obtained compound 5. The obtained compound was compound 5 as a result of mass spectrum analysis, and m/e=1062 with respect to a molecular weight of 1062.35.

Synthesis Example 6 (Synthesis of Compound 6)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(2-biphenylamino) synthesized by referring to the method described in WO 2010/122810 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that dibenzofuran was used to obtain compound 6. The obtained compound was compound 6 as a result of mass spectrum analysis, and m/e=1034 with respect to a molecular weight of 1034.39.

Synthesis Example 7 (Synthesis of Compound 7)

In the step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(2-tolylamino)di synthesized by referring to the method described in WO 2010/122810 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that benzofuran was used to obtain compound 7. The obtained compound was compound 7 as a result of mass spectrum analysis, and m/e=910 with respect to molecular weight 910.36.

Synthesis Example 8 (Synthesis of Compound 8)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(3-tolylamino)di synthesized by referring to the method described in WO 2010/122810 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that benzofuran was used to obtain compound 8. The obtained compound was compound 8 as a result of mass spectrum analysis, and m/e=910 with respect to molecular weight 910.36.

Synthesis Example 9 (Synthesis of Compound 9)

In the step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(4-tolylamino)di synthesized by referring to the method described in WO 2010/122810 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except for using benzofuran to obtain compound 9. As a result of mass spectrum analysis, the obtained compound was compound 9, and it was m/e=910 with respect to molecular weight 910.36.

Synthesis Example 10 (Synthesis of Compound 10)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 4-(3-biphenylamino) synthesized by referring to the method described in WO 2010/122810 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that dibenzofuran was used to obtain compound 10. The obtained compound was compound 10 as a result of mass spectrum analysis, and m/e=1034 with respect to a molecular weight of 1034.39.

Synthesis Example 11 (Synthesis of Compound 11)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-phenyl-4-(phenylamino) synthesized by referring to the method described in WO 2010/122810 ) Except having used dibenzofuran, it produced similarly to the process (1-2) of Synthesis Example 1, and obtained compound 11. The obtained compound was compound 11 as a result of mass spectrum analysis, and m/e=1034 with respect to a molecular weight of 1034.39.

Synthesis Example 12 (Synthesis of Compound 12)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-(2-tolyl)-4 synthesized by referring to the method described in WO 2013/077406 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that -(phenylamino)dibenzofuran was used to obtain compound 12. The obtained compound was compound 12 as a result of mass spectrum analysis, and m/e=1062 with respect to the molecular weight of 1062.42.

Synthesis Example 13 (Synthesis of Compound 13)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-methyl-4-(phenylamino) synthesized by referring to the method described in WO 2013/077405 ) Except having used dibenzofuran, it produced similarly to the process (1-2) of Synthesis Example 1, and obtained compound 13. The obtained compound was compound 13 as a result of mass spectrum analysis, and m/e=910 with respect to molecular weight 910.36.

Synthesis Example 14 (Synthesis of Compound 14)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-(t-butyl)-4 synthesized by referring to the method described in WO 2013/077405 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that -(phenylamino)dibenzofuran was used to obtain compound 14. The obtained compound was compound 14 as a result of mass spectrum analysis, and m/e=994 with respect to molecular weight 994.45.

Synthesis Example 15 (Synthesis of Compound 15)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-(t-butyl)-4 synthesized by referring to the method described in WO 2013/077405 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that -(2-tolylamino)dibenzofuran was used to obtain compound 15. The obtained compound was compound 15 as a result of mass spectrum analysis, and m/e=1022 with respect to a molecular weight of 1022.48.

Synthesis Example 16 (Synthesis of Compound 16)

In step (1-2) of Synthesis Example 1, instead of 4-(4-isopropylphenylamino)dibenzofuran, 6-cyclohexyl-4-(phenyl) synthesized by referring to the method described in WO 2013/077405 Except for using amino) dibenzofuran, it was prepared in the same manner as in the step (1-2) of Synthesis Example 1 to obtain compound 16. The obtained compound was compound 16 as a result of mass spectrum analysis, and m/e=1046 with respect to a molecular weight of 1046.48.

Synthesis Example 17 (Synthesis of Compound 17)

According to the following scheme, compound 17 was synthesized.

In the step (1-2) of Synthesis Example 1, instead of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene, synthesized by referring to the method described in KR-10-2012-0083203 Preparation was carried out in the same manner as in the step (1-2) of Synthesis Example 1 except that 3,11-dibromo-13,13-diphenyldibenzo[a,c]fluorene was used to obtain compound 17. As a result of mass spectrum analysis, the obtained compound was compound 17, and it was m/e=1016 with respect to molecular weight 1016.43.

Synthesis Example 18 (Synthesis of Compound 18)

According to the following scheme, compound 18 was synthesized.

In the step (1-2) of Synthesis Example 1, instead of 5,9-dibromo-7,7-diphenylbenzo[c]fluorene, 3,10 synthesized with reference to the method described in US 2009/0267491 -Dibromo-13,13-dimethyldibenzo[a,i]fluorene was prepared in the same manner as in the step (1-2) of Synthesis Example 1 to obtain compound 18. The obtained compound was compound 18 as a result of mass spectrum analysis, and m/e=892 with respect to a molecular weight of 892.40.

Synthesis Example 19 (Synthesis of Compound 19)

According to the following scheme, compound 19 was synthesized.

(19-1) Synthesis of 2-(1-naphthyl)ethyl benzoate

Under argon atmosphere, 2-bromobenzoate ethyl (15.0 g), 1-naphthalene boronic acid (12.4 g), tetrakis (triphenylphosphine) palladium (0) (0.76 g), 2M sodium carbonate aqueous solution (144 mL) and tetra A mixture of hydrofuran (504 mL) was refluxed for 7.5 hours. The reaction was cooled to room temperature, extracted with ethyl acetate, and the obtained organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain ethyl 2-(1-naphthyl)benzoate (18.0 g). The yield was 99%.

(19-2) Synthesis of 2-[2-(1-naphthyl)phenyl]propan-2-ol

In an argon atmosphere, to a 30 mL solution of 2-(1-naphthyl)ethyl benzoate (3.0 g) synthesized in (19-1) in tetrahydrofuran at 50° C., a tetrahydrofuran solution (44 mL) of 0.99 M methyl magnesium bromide ) Was added, and the mixture was stirred for 6 hours. The reaction was ice-cooled, water 60 mL was added little by little, the reaction was quenched, extracted with toluene, and the obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product (3.03 g) of 2-[2-(1-naphthyl)phenyl]propan-2-ol was used as it is in the next step.

(19-3) Synthesis of 7,7-methylbenzo[c]fluorene

To a mixture of the crude 2-[2-(1-naphthyl)phenyl]propan-2-ol obtained in (19-2) (3.03 g) and 72 mL of acetic acid, 0.8 mL of concentrated sulfuric acid was added, and 7 at room temperature. Stirred for hours. 50 mL of water was added to the reaction solution, and extraction was performed with 100 mL of toluene. The obtained organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 7,7-methylbenzo[c]fluorene (1.10 g). The yield in the second step of (19-2) and (19-3) was 41%.

(19-4) Synthesis of compound 19

In Synthesis Example 1, the preparation was carried out in the same manner as in Synthesis Example 1, except that 7,7-methylbenzo[c]fluorene synthesized in (19-3) was used instead of 7,7-diphenylbenzo[c]fluorene. And obtained compound 19. The obtained compound was compound 19 as a result of mass spectrum analysis, and m/e=842 with respect to molecular weight 842.39.

Synthesis Example 20 (Synthesis of Compound 20)

According to the following scheme, compound 20 was synthesized.

(20-1) Synthesis of 5-bromo-7,7-dimethylbenzo[c]fluorene

Dimethylformamide (27 mL) of 7,7-dimethylbenzo[c]fluorene (4.0 g) obtained by the same operation as in Synthesis Example 19 (19-1) to (19-3) under an argon atmosphere To the solution, a solution of N-bromosuccinimide (3.0 g) in dimethylformamide (10 mL) was added dropwise, followed by stirring at room temperature for 17 hours. Water (50 mL) was added to the reaction solution, extraction was performed with toluene, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 5-bromo-7,7-dimethylbenzo[c]fluorene (5.0 g). The yield was 95%.

(20-2) Synthesis of compound 20

In an argon atmosphere, 5-bromo-7,7-dimethylbenzo[c]fluorene (1.53 g) synthesized in (20-1), 4-( 4-isopropylphenylamino)dibenzofuran (1.8g), trisdibenzylideneacetonedipalladium (0) (0.07g), sodium-t-butoxide (0.46g) was dissolved in 24 mL of toluene, and tri- A solution in which t-butylphosphine (48 mg) was dissolved in toluene (0.17 mL) was added, followed by stirring at 85°C for 8 hours. The reaction solution was cooled to room temperature, filtered through celite to evaporate the solvent, and the obtained residue was purified by silica gel column chromatography and recrystallization to obtain 1.65 g (yield 64%) of compound 20. As a result of mass spectrum analysis, the obtained compound was compound 20, and it was m/e=543 with respect to molecular weight 543.26.

Synthesis Example 21 (Synthesis of Compound 21)

In Synthesis Example 20, instead of using 7,7-dimethylbenzo[c]fluorene, 13,13-dimethyldibenzo[a,g]fluid synthesized with reference to the method described in US 2009/0267491 Preparation was carried out in the same manner as in Synthesis Example 20 except that orene was used to obtain compound 21. The obtained compound was compound 21 as a result of mass spectrum analysis, and m/e=593 with respect to molecular weight 593.27.

Example 1

(Manufacture of organic EL device)

A glass substrate with an ITO transparent electrode having a thickness of 25 mm x 75 mm x 1.1 mm in thickness (manufactured by Geomatech Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.

The following compound (HI-1) was deposited by mounting the cleaned glass substrate with the ITO transparent electrode line on the substrate holder of the vacuum evaporation apparatus, and covering the transparent electrode on the side where the ITO transparent electrode line is formed. Thus, an HI-1 film having a thickness of 5 nm was formed to form a hole injection layer.

Next, on this hole injection layer, the following compound HT-1 was vapor-deposited as a first hole transport material to form an HT-1 film having a thickness of 110 nm to form a first hole transport layer.

Next, on this first hole transport layer, the following compound HT-2 was vapor-deposited to form a 15 nm-thick HT-2 film to form a second hole transport layer.

Next, compound BH-1 (host material) and compound 1 (dopant material) were co-deposited on the second hole transport layer to form a co-deposited film having a thickness of 25 nm. The concentration of compound 1 was 5.0% by mass. This co-deposited film functions as a light emitting layer.

Next, on this light-emitting layer, the following compound ET-1 was vapor-deposited to form an ET-1 film having a thickness of 10 nm to form a first electron transport layer.

Next, on this first electron transport layer, the following compound ET-2 was vapor-deposited to form an ET-1 film having a thickness of 15 nm to form a second electron transport layer.

Next, on this second electron transport layer, LiF was vapor-deposited at a film formation rate of 0.01 nm/sec to form a 1 nm-thick LiF film to form an electron-injecting electrode (cathode).

Then, metal Al was deposited on the LiF film to form a metal Al film having a thickness of 80 nm to form a metal Al cathode.

(Evaluation of organic EL device)

To the prepared organic EL device, a ^{voltage was applied so that the current density was 10 mA/cm 2} , and the driving voltage, the emission peak wavelength, and the external quantum efficiency were measured. In addition, when driving at a current density of 10 mA/cm ² , the time until the light emission luminance becomes 90% of the initial luminance (the luminance 90% lifetime) was evaluated. Table 1 shows the results.

Examples 2-18

In Example 1, a device was prepared and evaluated in the same manner as in Example 1 except that the compound shown in Table 1 was used instead of the compound 1. Table 1 shows the results.

Comparative Example 1

In Example 1, a device was prepared and evaluated in the same manner as in Example 1 except that the comparative example compound was used instead of the compound 1.

From the results of Table 1, it can be seen that the effect of the present invention is high efficiency, long life, and particularly excellent life performance. In the compound of the present invention, the structure of the compound is stabilized by introducing the cyclic structure shown in the formula (4) to the condensed fluorene derivative represented by the formula (2), which exhibits high luminescence properties, and as a result When driven as an organic EL device, high-efficiency light emission is obtained, and a long lifespan by suppressing deterioration of the device has become possible.

The amine compound of the present invention is useful as a material for realizing an organic EL device that has a long life and can be driven with high efficiency.

By using the material of the present invention as a dopant material for a light emitting layer, an organic EL device capable of driving with a long life and high efficiency is realized.

1: organic EL element
2: substrate
3: anode
4: cathode
5: light emitting layer
6: hole transport layer
7: electron transport layer
10: light-emitting unit

Claims (22)

An amine compound represented by the following formula (1).
[Formula (1)]

[In formula (1), n is an integer of 2, B is a structure represented by the following formula (2), A is an amine moiety represented by the following formula (4),
A is the same.
[Chemical Formula (2)]

In formula (2), at least one of the groups of ^{R 1} and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ^{8 is} Represents a bond hand to a divalent group represented by formula (3),
R ⁹ and R ¹⁰ each independently represent an unsubstituted C1-C5 alkyl group and an unsubstituted C6-C18 aryl group.
[Chemical Formula (3)]

In the formula (3), * represents a bonding site with a group representing a bond hand to a divalent group represented by formula (3) in the formula (2).
In formulas (2) and (3), ^{n of R 1} to ^{R 8} and R ¹¹ to ^{R 14} represents a bond with A,
In R ¹ to ^{R 8} and R ¹¹ to ^{R 14} , except for the above, each independently represents a hydrogen atom and an unsubstituted C 1 to C 5 alkyl group.
[Chemical Formula (4)]

In the formula (4), Ar ¹ represents a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms,
L ¹ and L ² each independently represent a single bond,
Any one of R ²¹ to ^{R 28 represents a bond with L 2} , and the others are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted cyclic carbon number of 3 to 6 Represents a cycloalkyl group of, or a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms,
X represents an oxygen atom,
** represents the binding site to B.
^{However, one} of the groups of R ^{1 and R 2} , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ is represented by the above formula (3). In the case of representing a bond hand to a divalent group,
^{As R 21 to R 28} contained in the above formula (4), at least one of those other than those representing a bond with L ² is each independently a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted It represents a cycloalkyl group having 3 to 6 ring carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms.
In the case of the'substituted or unsubstituted', the optional substituent is a cyano group, an alkylsilyl group having 1 to 5 carbon atoms, an arylsilyl group having 6 to 12 ring carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 6 It is an aryl group of ~12.] The method of claim 1,
In the formula (1), B is an amine compound represented by any one of the following formulas (11) to (13).
[Chemical Formulas (11)-(13)]

[In formulas (11) to (13), R ¹ to ^{R 14} are the same as those in formulas (2) and (3), respectively.] The method according to claim 1 or 2,
In the formula (2), in the group of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , two groups are An amine compound showing a bond hand to a divalent group represented by formula (3). The method according to claim 1 or 2,
In the above formula (1), B is an amine compound represented by any one of the following formulas (14) to (19).
[Chemical Formulas (14) to (19)]

[In formulas (14) to (19), R ¹ to ^{R 14} are the same as those in the formulas (2) and (3), ^{respectively, and R 11' to R 14'} are each of R ¹¹ to ^{R 14} Same as.] The method of claim 4,
In the formula (1), B is an amine compound represented by any one of formulas (14) to (16). The method according to claim 1 or 2,
An amine compound in the formula (1), wherein X is an oxygen atom. The method according to claim 1 or 2,
An amine compound in the formula (4), wherein L ¹ is a single bond. The method according to claim 1 or 2,
An amine compound in the formula (4), wherein L ² is a single bond. The method according to claim 1 or 2,
An amine compound in the formula (4), wherein R ²⁴ or R ²⁵ represents a bond with L ^2. The method according to claim 1 or 2,
In the formula (1), n is 1 or 2, the amine compound. The method according to claim 1 or 2,
^{Ar 1} in the formula (4) is a substituted or unsubstituted phenyl group, naphthyl group, or biphenylyl group. An organic electroluminescent device in which an organic thin film layer including at least one layer including a light emitting layer or a plurality of layers is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer contains the amine compound according to claim 1 alone or as a mixture. An organic electroluminescent device containing as a component of. The method of claim 12,
The organic electroluminescent device in which the light emitting layer contains the amine compound. The method of claim 12,
An organic electroluminescent device in which the at least one layer contains the amine compound according to any one of claims 1 or 2 and an anthracene derivative represented by the following formula (5).
[Chemical Formula (5)]

(In the formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, ,
R ¹⁰¹ to ^{R 108} are each independently a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, a combination of a monocyclic group and a condensed ring group A group consisting of, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted It is a group selected from an aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted silyl group, a halogen atom, and a cyano group.) The method of claim 14,
In the above formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted condensed cyclic group having 8 to 50 ring carbon atoms. The method of claim 14,
In the above formula (5), one of Ar ¹¹ and Ar ¹² is a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms, and the other is a condensation of 8 to 50 substituted or unsubstituted ring atoms. An organic electroluminescent device that is ventilation. The method of claim 14,
In the above formula (5), Ar ¹² is a naphthyl group, a phenanthryl group, a benzanthryl group, a 9,9-dimethylfluorenyl group, or a dibenzofuranyl group, and Ar ¹¹ is an unsubstituted or monocyclic group or An organic electroluminescent device in which the condensed cyclic group is a substituted phenyl group. The method of claim 14,
In the above formula (5), Ar ¹² is a substituted or unsubstituted condensed cyclic group having 8 to 50 ring atoms, and Ar ¹¹ is an unsubstituted phenyl group. The method of claim 14,
In the above formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 50 ring atoms. The method of claim 14,
In the formula (5), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted phenyl group. The method of claim 14,
In the above formula (5), Ar ¹¹ is an unsubstituted phenyl group, and Ar ¹² is a phenyl group having a monocyclic group or a condensed cyclic group as a substituent. The method of claim 14,
In the above formula (5), Ar ¹¹ and Ar ¹² are each independently a phenyl group having a monocyclic group or a condensed cyclic group as a substituent.

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