KR101688230B1 - Novel asymmetric arylamine derivatives for organic electroluminescent element, manufacturing method of the same, organic thin layer material and the organic electroluminescent element employing the same - Google Patents

Abstract

(상기 화학식 1에서 Ar은 탄소수 10 내지 20의 2가의 아릴기이고, Ar₁은 2가의 오각형고리를 포함하는 탄소수 2 내지 90의 아릴기로서 상기 오각형고리만의 탄소수가 5미만인 경우 비탄소자리는 질소, 산소, 황 또는 Si원소이며, Ar₂ 내지 Ar₅는 서로 독립적으로 같거나 다른 구조를 갖는 것으로 탄소수 6 내지 탄소수 30의 아릴기이며, 다만 Ar에서의 2급 아민과 3급 아민의 치환 위치가 대칭인 경우 Ar₂ 내지 Ar₅는 그 중 적어도 하나가 다른 구조를 갖는다.)
상기 화학식 1로 표현되는 중심구조의 아릴화합물인 Ar에 서로 다른 치환기가 도입된 비대칭 구조의 아릴아민유도체는 유기전기발광소자의 유기박막 형성시 이용 가능하며, 발광층 재료로, 특히 도펀트 재료로 사용하여 유기전기발광소자를 제작 시, 청색 파장 영역에서 우수한 발광 효율 특성을 나타낼 뿐만 아니라 우수한 수명 특성을 나타낸다.The present invention relates to an organic electroluminescent device having an asymmetric structure represented by the following general formula (1) in which a secondary amine and a tertiary amine are sequentially introduced into Ar, which is an aryl compound having a central structure, An organic thin film material for an organic electroluminescent device including the same, and an organic electroluminescent device using the same.
[Chemical Formula 1]

Wherein Ar is a divalent aryl group having 10 to 20 carbon atoms and Ar ₁ is an aryl group having 2 to 90 carbon atoms including a divalent pentagonal ring, and when the number of carbon atoms in the pentagonal ring is less than 5, And Ar ₂ to Ar ₅ independently represent an aryl group having 6 to 30 carbon atoms, which have the same or different structures, and the substitution position of the secondary amine and the tertiary amine in Ar Ar ₂ to Ar ₅ have at least one of them different structures.
The asymmetric arylamine derivative having different substituents introduced into Ar, which is an aryl compound of the central structure represented by Formula 1, can be used for forming an organic thin film of an organic electroluminescent device, and is used as a light emitting layer material, When the organic electroluminescence device is fabricated, it exhibits excellent luminescence efficiency characteristics in the blue wavelength region as well as excellent lifetime characteristics.

Description

TECHNICAL FIELD The present invention relates to novel arylamine derivatives for organic electroluminescent devices having novel asymmetric structures, methods for preparing the same, organic thin film materials for organic electroluminescent devices including the same, and organic electroluminescent devices using the same , organic thin layer material and the organic electroluminescent element employing the same}

The present invention relates to an arylamine derivative for an organic electroluminescent device having an asymmetric structure, a process for producing the same, an organic thin film material for the organic electroluminescent device including the arylamine derivative, and an organic electroluminescent device using the same.

Recently, as the demand for a flat display device with a small space occupation is increased due to enlargement of a display device, weight reduction and expansion of a viewing angle are emphasized. As a result, an organic electroluminescent device, which is a new flat display device which is advantageous in weight reduction, wide viewing angle, and fast response speed, is highlighted by using the self-luminescent phenomenon.

The organic electroluminescent device is a self-luminous device that utilizes the principle that a fluorescent material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. (CWTang, SAVanslyke, Applied Physics Letters, Vol. 51, p. 913, 1987, etc.) by laminated type devices by CWTang of Eastman Kodak Co., Studies on an organic electroluminescent device using a material have been actively carried out.

In the organic light emitting device, there have been many attempts to improve the lifetime by improving the blue light emitting material as a blue light emitting material which has the greatest influence on the lifetime thereof. Among them, the organic electroluminescent device is mainly developed by using a distyryl compound as an organic luminescent material and further adding styrylamine or the like (International Patent Publication No. 94-6175) Korean Patent Publication No. 2002-0070333 discloses a blue light emitting compound having a diphenyl anthracene structure and an aryl group substituted at the terminal thereof and an organic electroluminescent device using the blue light emitting compound. However, there is a problem that the luminous efficiency and brightness are not sufficient . US Pat. No. 6,854,229, Korean Patent Publication Nos. 2005-0107809 and 2006-0006760 disclose an organic electroluminescent device using a substituted pyrene-based compound, but the problem that the color purity of blue is low there was.

On the other hand, in order to realize a high-quality deep blue color, a phenanthracene derivative is used as a host material of a light emitting material (Japanese Patent Laid-Open No. 1996-012600), a material having a naphthyl group at 9,10 position of anthracene 1999-3782), and a method using an element material having a fluoranthene group at 9,10 position of anthracene (Japanese Patent Application Laid-Open No. 2001-257074). Although studies on the use of anthracene derivatives have been widely carried out, it is difficult to form a uniform thin film together with the problem of device lifetime, so that the film forming process is not excellent and heat resistance is not excellent. aggregation) occurs, and there is a problem in realizing long life with high efficiency and high-quality blue light emission.

Accordingly, it is an object of the present invention to provide an asymmetric arylamine derivative for organic electroluminescent devices capable of providing an organic electroluminescent device with high efficiency and long life by introducing an aryl group having an electron transporting ability.

It is another object of the present invention to provide a method for producing an arylamine derivative for an organic electroluminescence device having an asymmetric structure in which the arylamine derivative can be easily produced.

It is another object of the present invention to provide an organic thin film material for an organic electroluminescent device comprising an arylamine derivative for an asymmetric organic electroluminescent device.

Still another object of the present invention is to provide an organic electroluminescence device using the organic thin film material for the organic electroluminescent device.

In order to achieve the above object, the present invention is characterized by introducing a secondary amine and a tertiary amine as substituents to Ar, which is an aryl compound of a central structure, to be represented by the following chemical formula 1 so as not to have an axis of symmetry and a plane of symmetry in a molecule structure An arylamine derivative for an organic electroluminescence device having an asymmetric structure.

[Chemical Formula 1]

Wherein Ar is a divalent aryl group having 10 to 20 carbon atoms and Ar ₁ is an aryl group having 2 to 90 carbon atoms including a divalent pentagonal ring, and when the number of carbon atoms in the pentagonal ring is less than 5, And Ar ₂ to Ar ₅ independently represent an aryl group having 6 to 30 carbon atoms, which have the same or different structures, and the substitution position of the secondary amine and the tertiary amine in Ar Ar ₂ to Ar ₅ have at least one of them different structures.

In the compound represented by Formula 1, Ar is preferably selected from naphthalene, pyrene, perylene or pentacene.

The compound represented by Formula 1 is more preferably a compound represented by Formula 2 wherein Ar is naphthalene or a compound represented by Formula 3 wherein Ar is pyrene.

(2)

(In the formula 2, Ar ₁ is a non-carbon position is a nitrogen, oxygen, sulfur or Si, if the number of carbon atoms of only the pentagonal ring is less than 5 as a group of a carbon number of 2 to 90 containing a divalent pentagonal ring aryl, Ar ₂ to Ar ₅ is independently an aryl group having 6 to 30 carbon atoms, which is the same or different from each other, and Ar ₂ to Ar ₅ are at least a substituent in the case where the substitution position of the secondary amine and the tertiary amine in Ar is symmetric. One has a different structure.)

(3)

(In the formula 3 Ar ₁ is a non-carbon position is a nitrogen, oxygen, sulfur or Si, if the number of carbon atoms of only the pentagonal ring is less than 5 as a group of a carbon number of 2 to 90 containing a divalent pentagonal ring aryl, Ar ₂ to Ar ₅ is independently an aryl group having 6 to 30 carbon atoms, which is the same or different from each other, and Ar ₂ to Ar ₅ are at least a substituent in the case where the substitution position of the secondary amine and the tertiary amine in Ar is symmetric. One has a different structure.)

In the above formula (1), Ar ₁ represents an aryl group represented by the following formula (4), an aryl group represented by the formula (5), an aryl group represented by the formula (6), an aryl group represented by the formula An aryl group represented by formula (10), an aryl group represented by formula (11), and an aryl group represented by formula (11) and an aryl group in which at least two aryl groups of formula desirable.

[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , alkyl group, C ₂ ~ C ₄₀ alkenyl group, an alkoxy group of _{C 1 ~ C 40, C 3} ~ C 40 cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group or C ₆ of the To C ₄₀ heteroaryl group, and k is 1 or 3.)

[Chemical Formula 5]

(Hydrogen in the formula (5) independently of each of R ₁ and R _2, heavy hydrogen (deuterium), a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, a heteroaryl group, a C ₆ ~ C ₄₀ aryl group or a C ₆ ~ C ₄₀ of the, l is 1 or 3.)

[Chemical Formula 6]

(Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and m is 1 or 3.)

(7)

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , alkyl group, C ₂ ~ C ₄₀ alkenyl group, an alkoxy group of _{C 1 ~ C 40, C 3} ~ C 40 cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group or C ₆ of the To C ₄₀ heteroaryl group, and n is 1 or 3.)

[Chemical Formula 8]

Wherein R ₁ is selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and o is an integer of 1 to 3.)

[Chemical Formula 9]

(In the above formula (9), p is 1 or 2.)

[Chemical formula 10]

Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and q is 1 or 2.

(11)

Wherein R ₁ is selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and r is 1 or 2.

In the general formula (1), Ar ₂ to Ar ₅ are independently selected from the group consisting of an aryl group represented by the following general formula (12), an aryl group represented by the general formula (13), an aryl group represented by the general formula (14), an aryl group represented by the general formula Group, an aryl group represented by formula (17), an aryl group represented by formula (18), an aryl group represented by formula (19), and an aryl group represented by formula (12) It is preferably an aryl group.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms)

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ in Formula 1 may be substituted with at least one hydrogen atom independently of one another to form a group selected from the group consisting of deuterium, a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, , A cyano group, a trifluoromethyl group, an alkylsilyl group, an arylsilyl group with or without a heteroatom, or the like.

In order to accomplish another object of the present invention, the present invention provides a process for producing a compound represented by the following formula (1), which comprises subjecting an aryl compound disassociated to the same or different functional groups as a starting material to carry out an arylamination reaction or a Suzuki coupling reaction Wherein the functional group is sequentially substituted with a secondary amine or a tertiary amine group to produce an asymmetric compound represented by the above formula 1 having no symmetry axis or symmetry plane in the structure of the molecule, There is provided a process for producing an arylamine derivative.

[Reaction Scheme 1]

(In the above Reaction Scheme 1, X and Y are the same or different and each represents a functional group capable of arylamination, Ar is a divalent aryl group having 10 to 20 carbon atoms, Ar ₁ is a divalent aryl group having 2 to 5 carbon atoms, Carbon atoms of the pentagonal ring is less than 5, the non-carbon sites are nitrogen, oxygen, sulfur, or Si, Ar ₂ to Ar ₅ are independently of each other and have the same or different structures, and the number of carbon atoms is from 6 to 30 Provided that at least one of Ar ₂ to Ar ₅ has a different structure when the substitution position of the secondary amine and the tertiary amine in Ar is symmetrical.

In the above Reaction Scheme 1, Ar is preferably selected from naphthalene, pyrene, perylene or pentacene, more preferably naphthalene or pyrene as shown in the following Reaction Schemes 2 and 3.

[Reaction Scheme 2]

(Wherein X, Y, Ar ₁ to Ar ₅ are as defined in Reaction Scheme 1).

[Reaction Scheme 3]

(Wherein X, Y, Ar ₁ to Ar ₅ are as defined in Reaction Scheme 1).

In accordance with another aspect of the present invention, there is provided an organic thin film material for an organic electroluminescence device, which comprises an arylamine derivative for an organic electroluminescence device having an asymmetric structure represented by the general formula (1).

According to another aspect of the present invention, there is provided an organic electroluminescence device comprising a cathode, a cathode, and a plurality of organic thin film layers disposed between the anode and the cathode, And an arylamine derivative for an organic electroluminescence device having an asymmetric structure represented by the general formula (1).

The organic thin film layer may include at least one selected from a hole injecting layer, a hole transporting layer, a light emitting layer, an electron injecting layer, and an electron transporting layer. In particular, the organic thin film layer is preferably a light emitting layer. The organic thin film layer preferably contains a host compound and a dopant compound.

According to the present invention, a secondary amine having a central structure and a tertiary amine having a predetermined structure are introduced as a substituent into the aryl compound of the central structure, whereby an asymmetric organic electroluminescence having no symmetry axis and no symmetry plane in the molecular structure By providing an arylamine derivative for a device, when used in an organic electroluminescent device, excellent luminous efficiency and excellent lifetime characteristics can be obtained in the blue wavelength region.

1 is a view schematically showing a structure of an organic electroluminescence device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. The following detailed description is intended to illustrate the present invention by way of example, and thus the present invention is not limited thereto.

The present invention relates to an organic electroluminescent device having an asymmetric structure represented by the following general formula (1), which has no symmetry axis and a symmetry plane in a molecular structure by introducing a secondary amine and a tertiary amine into a central structure aryl compound as a substituent An arylamine derivative is provided.

[Chemical Formula 1]

Wherein Ar is a divalent aryl group having 10 to 20 carbon atoms and Ar ₁ is an aryl group having 2 to 90 carbon atoms including a divalent pentagonal ring, and when the number of carbon atoms in the pentagonal ring is less than 5, And Ar ₂ to Ar ₅ independently represent an aryl group having 6 to 30 carbon atoms, which have the same or different structures, and the substitution position of the secondary amine and the tertiary amine in Ar Ar ₂ to Ar ₅ have at least one of them different structures.

In the compound represented by Formula 1, Ar is preferably selected from naphthalene, pyrene, perylene or pentacene.

In particular, the compound represented by Formula 1 is more preferably a compound represented by Formula 2 wherein Ar is naphthalene, or a compound represented by Formula 3 wherein Ar is pyrene.

(2)

(In the formula 2, Ar ₁ is a non-carbon position is a nitrogen, oxygen, sulfur or Si, if the number of carbon atoms of only the pentagonal ring is less than 5 as a group of a carbon number of 2 to 90 containing a divalent pentagonal ring aryl, Ar ₂ to Ar ₅ is independently an aryl group having 6 to 30 carbon atoms, which is the same or different from each other, and Ar ₂ to Ar ₅ are at least a substituent in the case where the substitution position of the secondary amine and the tertiary amine in Ar is symmetric. One has a different structure.)

(3)

(In the formula 3 Ar ₁ is a non-carbon position is a nitrogen, oxygen, sulfur or Si, if the number of carbon atoms of only the pentagonal ring is less than 5 as a group of a carbon number of 2 to 90 containing a divalent pentagonal ring aryl, Ar ₂ to Ar ₅ is independently an aryl group having 6 to 30 carbon atoms, which is the same or different from each other, and Ar ₂ to Ar ₅ are at least a substituent in the case where the substitution position of the secondary amine and the tertiary amine in Ar is symmetric. One has a different structure.)

In the above formula (1), Ar ₁ represents an aryl group represented by the following formula (4), an aryl group represented by the formula (5), an aryl group represented by the formula (6), an aryl group represented by the formula An aryl group represented by formula (10), an aryl group represented by formula (11), and an aryl group represented by formula (11) and an aryl group in which at least two aryl groups of formula desirable.

[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , alkyl group, C ₂ ~ C ₄₀ alkenyl group, an alkoxy group of _{C 1 ~ C 40, C 3} ~ C 40 cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group or C ₆ of the To C ₄₀ heteroaryl group, and k is 1 or 3.)

[Chemical Formula 5]

(Hydrogen in the formula (5) independently of each of R ₁ and R _2, heavy hydrogen (deuterium), a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, a heteroaryl group, a C ₆ ~ C ₄₀ aryl group or a C ₆ ~ C ₄₀ of the, l is 1 or 3.)

[Chemical Formula 6]

(Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and m is 1 or 3.)

(7)

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , alkyl group, C ₂ ~ C ₄₀ alkenyl group, an alkoxy group of _{C 1 ~ C 40, C 3} ~ C 40 cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group or C ₆ of the To C ₄₀ heteroaryl group, and n is 1 or 3.)

[Chemical Formula 8]

Wherein R ₁ is selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and o is an integer of 1 to 3.)

[Chemical Formula 9]

(In the above formula (9), p is 1 or 2.)

[Chemical formula 10]

Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and q is 1 or 2.

(11)

Wherein R ₁ is selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group or a C ₆ to C ₄₀ heteroaryl group, and r is 1 or 2.

In the general formula (1), Ar ₂ to Ar ₅ are independently selected from the group consisting of an aryl group represented by the following general formula (12), an aryl group represented by the general formula (13), an aryl group represented by the general formula (14), an aryl group represented by the general formula Group, an aryl group represented by formula (17), an aryl group represented by formula (18), an aryl group represented by formula (19), and an aryl group represented by formula (12) It is preferably an aryl group.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms)

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ in Formula 1 may be substituted with at least one hydrogen atom independently of one another to form a group selected from the group consisting of deuterium, a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, , A cyano group, a trifluoromethyl group, an alkylsilyl group, an arylsilyl group with or without a heteroatom, or the like.

Specific examples of the compound represented by the above formula (2) wherein Ar is naphthalene in the compound represented by the above formula (1) include the compounds represented by the following formulas (20) to (27). However, the present invention is not limited thereto.

<Naphthalene Derivative>

Specific examples of the compound represented by Formula 3 wherein Ar is pyrene in the compound represented by Formula 1 include the compounds represented by Formula 28 to 59 shown below. However, the present invention is not limited thereto.

<Pyrene Derivative>

A method for synthesizing an asymmetric arylamine derivative for an organic electroluminescence device having a symmetry axis and a symmetry plane in one molecule represented by the formula (1) according to the present invention is characterized in that, as shown in the following Reaction Scheme 1, It can be easily prepared by substituting the functional group sequentially with a secondary amine or a tertiary amine group through a known aryl amination reaction or a Suzuki coupling reaction using an aryl compound having a central structure as a starting material.

[Reaction Scheme 1]

(In the above Reaction Scheme 1, X and Y are the same or different and each represents a functional group capable of arylamination, Ar is a divalent aryl group having 10 to 20 carbon atoms, Ar ₁ is a divalent aryl group having 2 to 5 carbon atoms, Carbon atoms of the pentagonal ring is less than 5, the non-carbon sites are nitrogen, oxygen, sulfur, or Si, Ar ₂ to Ar ₅ are independently of each other and have the same or different structures, and the number of carbon atoms is from 6 to 30 Provided that at least one of Ar ₂ to Ar ₅ has a different structure when the substitution position of the secondary amine and the tertiary amine in Ar is symmetrical.

In the above Reaction Scheme 1, Ar is preferably selected from naphthalene, pyrene, perylene or pentacene, more preferably naphthalene or pyrene as shown in the following Reaction Schemes 2 and 3.

[Reaction Scheme 2]

(Wherein X, Y, Ar ₁ to Ar ₅ are as defined in Reaction Scheme 1).

[Reaction Scheme 3]

(Wherein X, Y, Ar ₁ to Ar ₅ are as defined in Reaction Scheme 1).

In the above Reaction Scheme 1, X and Y are preferably selected from halogen, amine, and hydroxyl groups, but not limited thereto. Any functional group capable of introducing different substituents through sequential reactions is included in the present invention.

For example, the asymmetric arylamine derivative represented by Formula 1 according to the present invention may be an aryl compound disassociated to the same or different functional groups, for example, the same or different halogens, halogens and amines, Or an aryl compound having a central structure having a halogen and a hydroxyl group as starting materials and sequentially reacting the starting material with an arylamine or a boronic acid of an arylamine, an asymmetric structure compound can be easily obtained.

Aryl-aryl coupling reaction of an arylamine and an arylhalogen compound for introducing a secondary amine and a tertiary amine to provide an arylamine compound having a central structure disassociated to the same or different functional groups has heretofore been reported And an arylamine derivative represented by the general formula (1) according to the present invention can be easily produced by carrying out the reaction under the reaction conditions described above. Particularly, in addition to the reaction using copper (Cu) (Canadian Journal Chemistry, 61, 1983, 86 to 91) and the reaction using t-BuOK (Organic Letters, 5, 19, 2003, 3515 to 3518) (Organic Letters, 7, 11, 2005, 2209-2211) and reactions using palladium catalysts (Journal of Organic Chemistry, 64, 15, 1999, 5575-5580).

(Suzuki coupling reaction in which an amino group is introduced through a boronic acid-sialylation reaction) have been reported so far (Refer to Chem. Rev., Vol. 95, No. 7, 2457 (1995), etc.) The reaction conditions described can also be carried out. The Suzuki coupling reaction is usually carried out under an inert atmosphere such as nitrogen, argon, helium or the like under atmospheric pressure. However, the Suzuki coupling reaction can also be carried out under a pressurized condition if necessary. The reaction temperature is in the range of 15 to 300 占 폚, particularly preferably 30 to 200 占 폚.

According to an embodiment of the present invention, the asymmetric arylamine derivative represented by Formula 1 may be prepared by a boronic acid-based reaction, and the boronic acid-based reaction may be carried out by a known method Lecture 4, Volume 24, pages 61 to 90 and J. Org. Chem., Vol. 60, 7508 (1995)).

The arylamine used for synthesizing the arylamine derivative compound having an asymmetric structure represented by the general formula (1) by introducing different substituents to the arylamine compound disassociated to the same or different functional groups is a compound having a structure selected from the following formulas May be used. As the arylboronic acid, compounds having a structure selected from the following formulas (58) to (81) may be used, but the present invention is not limited thereto.

<Arylamine>

<Arylboronic Acid>

Asymmetric arylamine derivatives represented by formula (I) according to the present invention, in which a secondary amine and a tertiary amine are introduced into an aryl compound having a central structure as described above so as not to have a symmetry axis and a symmetry plane in one molecule, The blue luminous efficiency and the longevity of blue luminous efficiency can be improved compared with the conventional arylamine derivatives having the same secondary amine or tertiary amine introduced in the prior art.

Hereinafter, an organic thin film material for an organic electroluminescent device and an organic electroluminescent device according to the present invention will be described.

The present invention provides an organic thin film material for an organic electroluminescence device comprising an arylamine derivative having an asymmetric structure represented by the general formula (1). Any organic thin film material for an organic electroluminescence device containing an arylamine derivative having an asymmetric structure represented by the above formula (1) is included in the present invention.

According to the present invention, the organic thin film material comprising an arylamine derivative having an asymmetric structure represented by Formula 1 is preferably a light emitting material or a dopant material.

Since the organic thin film material for an organic electroluminescent device other than the arylamine derivative having an asymmetric structure of Formula 1 according to the present invention is well known in the art, a detailed description thereof will be omitted. However, An explanation is given in the explanation of the example.

An organic electroluminescent device according to the present invention includes an anode, a cathode, and a plurality of organic thin film layers positioned between the anode and the cathode, wherein at least one of the organic thin film layers includes an organic electroluminescent Organic thin film materials for organic EL devices.

The organic thin film layer includes at least one selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer. More preferably, the organic thin film layer including the organic thin film material for an organic electroluminescent device is a light emitting layer.

A more concrete example is as follows.

1 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. As shown in the figure, the substrate 1, the anode 2, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, and the cathode 7 may be provided. An electron injection layer (not shown) may be further provided between the electron transport layer 6 and the cathode 7 and a hole injection layer 3 may be further provided between the anode 2 and the hole transport layer 4. [

Here, the hole injecting layer 3, the hole transporting layer 4, the light emitting layer 5, the electron transporting layer 6, the electron injecting layer (not shown in the figure), etc., which can be placed between the anode 2 and the cathode 7 And an organic thin film material including an asymmetric arylamine derivative represented by the general formula (1) may be included in all or a part of the organic thin film layer.

Examples of the anode (2) material include metal oxides or metal nitrides such as ITO, IZO, tin oxide, zinc oxide, zinc aluminum oxide, and titanium nitride; Metals such as gold, platinum, silver, copper, aluminum, nickel, cobalt, lead, molybdenum, tungsten, tantalum and niobium; An alloy of such a metal or an alloy of copper iodide; And conductive polymers such as polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, poly (3-methylthiophene), and polyphenylene sulfide. The anode 2 may be formed of only one of the above-mentioned materials or may be formed of a mixture of a plurality of materials. Further, a multi-layer structure composed of a plurality of layers of the same composition or different compositions may be formed.

The hole injecting layer 3 of the present invention can be made of materials known in the art including, but not limited to PEDOT / PSS or copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylphenylamino) A material such as triphenylamine (m-MTDATA) and 4,4 ', 4 "-tris (N- (2-naphthyl) -N- phenylamino) -triphenylamine (2-TNATA) May be formed to have a predetermined thickness. If necessary, the hole injection layer 3 may contain an arylamine derivative represented by Formula 1 according to the present invention.

The hole transport layer 4 may be formed of a material known in the art such as 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD). If necessary, the hole transport layer 4 may contain the arylamine derivative represented by Formula 1 according to the present invention.

The light emitting layer 5 may include an arylamine derivative represented by Formula 1 according to the present invention. The light emitting layer 5 may be formed of a fluorescent and phosphorescent host and a dopant material known in the art. Here, the content of the arylamine derivative represented by the formula (1) according to the present invention may be added within the range of the conventional fluorescent and phosphorescent dopants.

The host material of the light emitting layer is not limited, but 4,4'-N, N-dicarbazolebiphenyl (CBP) and 1,3-N, N-dicarbazole benzene (mCP) and derivatives thereof can be used. In recent years, it has been known that BAlq having electron transportability or Al complex materials similar thereto is useful as a phosphorescent host. Specifically, it is known that 4,4'-bis (2,2-diphenyl-ethen-1-yl) Bis (2-methyl-8-quinolinolato) (triphenylsiloxy) aluminum (III) (SAlq), bis (2-methyl-8 (Quinolinolato) (para-phenolato) aluminum (III) (BAlq), bis (salen) zinc (II), 1,3-bis [4- (N, , 4-oxadiazoyl] benzene (OXD8), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,2 ', 7,7' -Tetrakis (non-phenyl-4-yl) -9,9'-spirofluorene (Spiro-DPVBI), tris (para- Bis (dimetylboryl) -2,2-bithiophene (BMB-2T) and perylene can be used.

(4-dicyanomethylene-2-methyl-6- (para-dimethylaminostyryl) -4H-pyran), DCM2 (4- (Dicyanomethylene) -2-methyl-6- (1,1, 7, -dichloromethyl) 9H-pyran), DCJTB (4- (dicyanomethylene) -2-tertiarybutyl-6- (1,1,7,7-tetramethylpyrrolidyl -9-enyl) -4H-pyran, DCJTI (4-dicyanomethylene) -2-isopropyl-6- (1,1,7,7-tetramethyljulolidyl- ) And Nile red, Rubrene and the like can be used as a host or a dopant.

The host and the dopant may be used singly or in combination of two or more when added.

The electron transport layer 6 may comprise aryl-substituted oxadiazole, aryl-substituted triazole, aryl-substituted phenanthroline, benzoxazole, or benzothiazole compounds which are materials known in the art. More specifically, the electron transport layer 6 is formed of a material selected from the group consisting of 1,3-bis (N, N-t-butyl-phenyl) -1,3,4-oxadiazole (OXD-7); 3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4-triazole (TAZ); 2,9-dimethyl-4,7-diphenyl-phenanthroline (basocuproin or BCP); Bis (2- (2-hydroxyphenyl) -benzoxazolate) zinc; Or bis (2- (2-hydroxyphenyl) -benzothiazolate) zinc; The electron transporting material is formed using at least one compound selected from (4-biphenyl) (4-t-butylphenyl) oxydiazole (PDB) and tris (8- quinolinato) aluminum , And may preferably be formed including tris (8-quinolinato) aluminum (III) (Alq3). If necessary, the electron transport layer 6 may include an arylamine derivative having an asymmetric structure represented by Formula 1 according to the present invention.

The electron injection layer and the cathode 7 may be formed using materials known in the art, including, but not limited to, LiF, and the cathode may have a low work function such as Al, Ca, Mg, or Ag Metal, and may be formed preferably including Al.

The organic electroluminescent device according to the present invention can be applied to various display devices. The display device may be a display device using a backlight unit, and the organic electroluminescent device may be used as a light source and a single light source of the backlight unit. In addition, the display device may be an organic electroluminescent display (OLED).

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples. Particularly, in the synthesis examples, some of the compounds are synthesized, but other compounds are also synthesized through the same synthetic route. According to the present invention or known method, any one of ordinary skill in the art will understand that any compound having no symmetry axis or a non- It is possible to synthesize an arylamine derivative having an asymmetric structure, and thus the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Compound (20)

The overall synthesis procedure is shown in Scheme 4 below.

First, a 250 mL three-necked flask was charged with 5.00 g (15.0 mmol) of 6-bromo-1-iodo-naphthalene and 1-methyl-5- (naphthalen- (Triphenylphosphine) -palladium was added to the reaction mixture, and 60 mL of 1,2-dimethoxyethane and 30 mL of a 2M sodium carbonate aqueous solution were added thereto, followed by reflux at 95 ° C. for 18 hours . After the completion of the reaction, the reaction temperature was cooled to room temperature, the organic layer was extracted with distilled water and ethyl acetate, dried over magnesium sulfate, and the solvent was removed under reduced pressure, followed by reprecipitation using tetrahydrofuran and methanol. After drying under vacuum, 5- (6-bromonaphthalene-2-yl) -1-methyl-N- (naphthalen- ) (calcd for C ₃₁ H ₂₃ BrN ₂ , 502.10; Found: 502) in a yield of 4.43 g (68%).

Then, a 250 mL three-necked flask was charged with 5- (6-bromonaphthalene-2-yl) -1-methyl-N- (naphthalen- (Dibenzylideneacetone) -palladium and tri-t-butylphosphine, sodium-tertiary-butylphosphine, and a catalytic amount of 2,6- t-butoxide was added thereto, and 80 mL of toluene was added thereto, followed by stirring at room temperature for 5 hours. After the completion of the reaction, the reaction temperature was lowered to room temperature, and the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure, followed by reprecipitation using tetrahydrofuran and methanol. After drying under vacuum, 1-methyl-5- [6- (naphthalen-1-yl- (naphthalen-2-yl) amino) naphthalen- Phenyl-1-pyrrole-2-amine (4.43 g, 81%).

MS (EI) (calcd for C ₄₇ H ₃₅ N ₃ , 641.80; Found: 641)

[Reaction Scheme 4]

Synthesis Example 2 Synthesis of Compound (21)

The overall synthesis procedure is shown in Reaction Scheme 5 below. As shown in Reaction Scheme 5, the Suzuki coupling reaction of Synthesis Example 1 yields 1-methyl-5- (naphthalen-2-yl- phenylamino) (6-bromonaphthalen-2-yl) -N- (naphthalene-2-carboxylic acid) was prepared using 5- (naphthalen-2-yl (phenyl) amino) thiophene- 2-yl) -N-phenylthiophene-2-amine. After the synthesis of arylamine, N, N-phenylnaphthalen-1- (80%) of (naphthalene-1-yl- (naphthalen-2-yl) amino) naphthalen-2-yl] -N- &Lt; / RTI &gt;

MS (EI) (calcd for C ₄₆ H ₃₂ N ₂ S, 644.82; Found: 644)

 [Reaction Scheme 5]

Synthesis Example 3 Synthesis of Compound (28)

The overall synthesis procedure is shown in Scheme 6 below.

First, a 500 mL three-necked flask was charged with 16.20 g (45.0 mmol) of 1,6-dibromopyran and 5-methyl-4- (naphthalen-2-yl- phenylamino) 1.93 g (5.62 mmol) of nickel acide and a catalytic amount of tetrakis (triphenylphosphine) -palladium were charged, 225 mL of 1,2-dimethoxyethane and 60 mL of a 2M sodium carbonate aqueous solution were added, and the mixture was refluxed at 95 ° C. for 18 hours. After completion of the reaction, the reaction temperature was cooled to room temperature, excess dibromoprene was recovered by filtration, and the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried with magnesium sulfate, the solvent was removed under reduced pressure and then tetrahydrofuran and methanol Lt; / RTI &gt; and filtered. After drying in vacuo, the objective compound 5- (6-bromopyran-1-yl) -1-methyl-N- (naphthalen- ) (calcd for C ₃₇ H ₂₅ BrN ₂ , 576.12; Found: 576) in a yield of 2.8 g (84%).

Then, a 250 mL three-necked flask was charged with 5- (6-bromopyran-1-yl) -1-methyl-N- (naphthalen- 1.12 g (4.16 mmol) of 2-amine (3.46 mmol), N- (naphthalen-2-yl) naphthalen-1-amine and a catalytic amount of bis (dibenzylidineacetone) -palladium and tri- Phosphine and sodium-t-butoxide were added, 80 mL of toluene was added, and the mixture was stirred at 105 캜 for 5 hours. After the completion of the reaction, the reaction temperature was lowered to room temperature, and the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure, followed by reprecipitation using tetrahydrofuran and methanol. After drying under vacuum, 1-methyl-5- (6- (naphthalen-1-yl- (naphthalen-2-yl) amino) Phenyl-1H-pyrrole-2-amine was obtained in a yield of 2.33 g (73%).

MS (EI) (calcd for C ₅₇ H ₃₉ N ₃ , 765.31; Found: 765)

[Reaction Scheme 6]

Synthesis Example 4 Synthesis of Compound (29)

The overall synthetic procedure is shown in Scheme 7 below, and as shown in Scheme 7, the synthesis of 5-methyl-4- (naphthalen-2-yl- phenyl-amino) Yl) -N- (2-methoxyphenyl) amino] thiophene-2-ylboronic acid was prepared using 5- (naphthalen- (Naphthalen-2-yl) -N-phenylthiophene-2-amine was synthesized and N- (naphthalen-2-yl) naphthalen- 1 -amineamine of Synthesis Example 3 was used for the arylamination reaction 1-yl) -N- (naphthalen-2-yl) -N-phenylthiophene-2 -Amine in a yield of 2.22 g (70%).

MS (EI) (calcd for C ₅₆ H ₃₆ N ₂ S, 768.26; Found: 768)

[Reaction Scheme 7]

Synthesis Example 5 Synthesis of Compound (30)

The overall synthesis procedure is shown in Scheme 8 below, and as shown in Scheme 8, the synthesis of 5-methyl-4- (naphthalen-2-yl- phenylamino) (6-Bromopyran-1-yl) -amine was prepared using l-methyl-2- (naphthalen-2-yl (Naphthalene-2-yl) -N-phenyl-1H-imidazol-2-amine was synthesized in the same manner as in Synthesis Example 3, 2-yl) naphthalen-l-amine, the final object, 1-methyl-5- (6- (naphthalen- - (naphthalen-2-yl) -N-phenyl-1H-imidazol-2-amine in a yield of 1.99 g (68%).

MS (EI) (calcd for C ₅₆ H ₃₈ N ₄ , 766.31; Found: 766)

[Reaction Scheme 8]

Synthesis Example 6 Synthesis of Compound (32)

The overall synthetic procedure is shown in Reaction Scheme 9 below, and as shown in Scheme 9, the Suzuki coupling reaction of Synthesis Example 3 is repeated using 5-methyl-4- (naphthalen-2-yl- phenylamino) 5- (6-Fluorophenyl) amino-4H-1,2,4-triazol-3-ylboronic acid instead of the Nickel acid Yl) -4-methyl-N- (naphthalen-2-yl) -N-phenyl-4H-1,2,4- triazol- Methyl-5- (6- (naphthalen-2-yl) naphthalene-1-amine of synthesis example 3, Yl) -N- (naphthalen-2-yl) -N-phenyl-4H-1,2,4-triazole-3-amine was obtained in a yield of 2.05 g (69%).

MS (EI) (calcd for C ₅₅ H ₃₇ N ₅ , 767.30, Found: 767)

 [Reaction Scheme 9]

Comparative Synthesis Example 1 Synthesis of Compound (96)

The overall synthesis procedure is shown in Scheme 10 below.

In a 100 mL three-necked flask, 2.00 g (5.6 mmol) of 1,6-dibromopyrene, 1.90 g (11.2 mmol) of diphenylamine, and a catalytic amount of bis (dibenzylidineacetone) t-Butylphosphine and sodium-t-butoxide were added, 40 mL of toluene was added, and the mixture was stirred at room temperature for 8 hours. After the completion of the reaction, the reaction temperature was lowered to room temperature, and the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure, followed by reprecipitation using tetrahydrofuran and methanol. N, N, N ', N'-tetraphenyl-pyrene-1,6-diamine (Formula 96) in which the same secondary amine as the objective product was substituted was obtained in a yield of 2.35 g (74%) after vacuum drying.

MS (EI) (calcd for C ₄₀ H ₂₈ N ₂ , 536.66; Found: 535)

[Reaction Scheme 10]

Example 1: Fabrication and evaluation of organic electroluminescent device 1

A glass substrate with an ITO transparent electrode coated with an insulating film so that it could be fabricated with a 22 mm x 2 mm unit was ultrasonically cleaned in isopropyl alcohol for 5 minutes and then subjected to UV ozone cleaning for 30 minutes. After the cleaned glass substrate with the transparent electrode line was mounted on the substrate holder of the vacuum evaporation apparatus, 2-TNATA (4,4 '') hole injection material was formed so as to cover the transparent electrode on the side where the transparent electrode line was formed. , 4 "-Tris (N- (2-naphthyl) -N-phenyl-amino) -tri-phenylamine was deposited to a thickness of 600 Å by resistance heating deposition. bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine) was deposited to a thickness of 200 Å by the same deposition method. After the compound of Formula 20 prepared in Example 1 was doped with a fluorescent dopant (3 wt%) to a thickness of 40 nm, Alq3 (tris- (8-hydroxyquinoline) aluminum- (III) A Li film was formed thereon to a film thickness of 10 nm at a deposition rate of 1.5 ANGSTROM / sec: 1 ANGSTROM / min, and Al was deposited on the Li film A metal cathode having a thickness of 100 nm was formed to fabricate an organic electroluminescent device. The equipment used for the deposition was an EL evaporator of VTS.

[Formula 97]

Example 2: Fabrication and evaluation of organic electroluminescence device 2

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compound of Formula 21 prepared in Synthesis Example 2 was used instead of the compound of Formula 20 prepared in Synthesis Example 1.

Example 3: Fabrication and evaluation of organic electroluminescent device 3

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compound of Formula 28 prepared in Synthesis Example 3 was used instead of the compound of Formula 20 prepared in Synthesis Example 1. [

Example 4: Fabrication and evaluation of organic electroluminescent device 4

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compound of Formula 29 prepared in Synthesis Example 4 was used instead of the compound of Formula 20 prepared in Synthesis Example 1.

Example 5: Fabrication and evaluation of organic electroluminescent device 5

An organic electroluminescence device was fabricated in the same manner as in Example 1, except that the compound of Formula 30 prepared in Synthesis Example 5 was used instead of the compound of Formula 20 prepared in Synthesis Example 1.

Example 6: Fabrication and evaluation of organic electroluminescent device 6

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compound of Formula 32 prepared in Synthesis Example 6 was used instead of the compound of Formula 20 prepared in Synthesis Example 1.

Comparative Example 1: Fabrication and evaluation of organic electroluminescent device 11

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compound of Formula 96 prepared in Comparative Synthesis Example 1 was used instead of the compound of Formula 20 prepared in Synthesis Example 1.

<Experimental Example>

The organic electroluminescent devices manufactured in Examples 1 to 6 and Comparative Example 1 were subjected to the characteristic evaluation in the following manner, and the results are shown in Table 1.

1) Current density

The organic electroluminescent device manufactured was measured for the change of the current density according to the voltage change. The measurement was carried out by using a current-voltmeter (Kethely 237) while increasing the current density from 2.5 mA / cm ² to 100 mA / cm ² by 2.5 mA.

2) Color coordinates

The prepared organic electroluminescent device was measured using a luminance meter (PR650) while increasing the current density from 2.5 mA / cm ² to 100 mA / cm ² by 2.5 mA.

3) Luminance

The power was supplied from a current-voltmeter (Kethley SMU 236) and measured using a luminance meter (PR650).

4) Efficiency

The luminous efficiency was calculated using the luminance and current density measured above.

Current density
(mA / cm 2) Color coordinates CIE1931
(x, y) efficiency
(cd / A) life span
(@ 1000nit) Example 1 20 (0.144, 0.123) 2.82 400 Example 2 20 (0.142, 0.109) 2.47 150 Example 3 20 (0.149, 0.118) 3.52 250 Example 4 20 (0.144, 0.143) 5.28 400 Example 5 20 (0.142, 0.155) 5.57 600 Example 6 20 (0.143, 0.156) 5.43 520 Comparative Example 1 20 (0.173, 0.164) 4.29 60

As can be seen from the results of Table 1, the asymmetric structure in which different secondary amines and tertiary amines are substituted for the aryl compound of the central structure as substituents so as not to have the symmetry axis and the symmetry plane in the molecule represented by the formula Can be used for forming an organic thin film layer of an organic electroluminescent device and can be used as a light emitting layer to emit light in the blue wavelength region when the organic electroluminescent device is fabricated and exhibit excellent color purity as compared with a material having a symmetric structure, It can be confirmed that the characteristics are improved.

1: substrate 2: anode
3: Hole injection layer 4: Hole transport layer
5: luminescent layer 6: electron transport layer
7: cathode

Claims (15)

The organic EL device according to any one of claims 1 to 3, wherein the aryl group of the asymmetrically structured organic electroluminescence device is represented by the following formula (1), wherein a secondary amine and a tertiary amine are substituted as a substituent group in Ar, Amine derivatives.
[Chemical Formula 1]

Wherein Ar is a compound represented by the following general formula (2) or a compound represented by the following general formula (3), Ar ₁ is a heteroaryl group represented by any one of formulas (4) to (6) oxygen, and sulfur or a Si element, Ar ₂ to Ar ₅ is a heteroaryl group containing an aryl group, or an N having 6 to carbon atoms, 30 to be the same, independently of each other, or having a different structure, Ar ₂ to Ar ₅ is of the At least one has a different structure.)
(2)

(3)

[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , An alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, or a C ₆ to C ₄₀ aryl group, and k is 1 or 3.
[Chemical Formula 5]

(Hydrogen in the formula (5) independently of each of R ₁ and R _2, heavy hydrogen (deuterium), a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ aryl group and the cycloalkyl in the alkyl group, or C ₆ ~ C ₄₀ of, l is 1 or 3.)
[Chemical Formula 6]

(Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, or a C ₆ to C ₄₀ aryl group, and m is 1 or 3.)
delete delete delete The compound according to claim 1, wherein Ar ₂ to Ar ₅ in the formula (1) are selected from the group consisting of an aryl group represented by the following general formula (12), an aryl group represented by the general formula (13), an aryl group represented by the general formula (14), a heteroaryl group represented by the general formula At least two aryl groups of the heteroaryl group represented by the formula (16), the heteroaryl group represented by the formula (17), the aryl group represented by the formula (18), the aryl group represented by the formula (19) and the aryl group represented by the formula And the aryl group is an aryl group selected from the group consisting of aryl groups bonded to each other.
[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms)
delete As shown in Reaction Scheme 1, Ar is used as a starting material, which is an aryl compound of a central structure disassociated to the same or different functional groups, and functional groups are sequentially introduced through a Suzuki-coupling reaction, Or a tertiary amine group to produce an asymmetric compound represented by the following Formula 1 having no symmetry axis and no symmetry plane in the structure of the molecule.
[Chemical Formula 1]

Wherein Ar is a compound represented by the following general formula (2) or a compound represented by the following general formula (3), Ar ₁ is a heteroaryl group represented by any one of formulas (4) to (6) oxygen, and sulfur or a Si element, Ar ₂ to Ar ₅ is a heteroaryl group containing an aryl group, or an N having 6 to carbon atoms, 30 to be the same, independently of each other, or having a different structure, Ar ₂ to Ar ₅ is of the At least one has a different structure.)
(2)

(3)

[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ , An alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, or a C ₆ to C ₄₀ aryl group, and k is 1 or 3.
[Chemical Formula 5]

(Hydrogen in the formula (5) independently of each of R ₁ and R _2, heavy hydrogen (deuterium), a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ aryl group and the cycloalkyl in the alkyl group, or C ₆ ~ C ₄₀ of, l is 1 or 3.)
[Chemical Formula 6]

(Wherein R ₁ is hydrogen, deuterium, halogen, amino, nitrile, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₁ to C ₄₀ alkoxy , A C ₃ to C ₄₀ cycloalkyl group, or a C ₆ to C ₄₀ aryl group, and m is 1 or 3.)

[Reaction Scheme 1]

(Wherein X and Y are the same or different from each other and selected from a halogen, an amine or a hydroxy group, and Ar, Ar ₁ , Ar ₂ to Ar ₅ are as defined above)
delete delete An organic thin film material for an organic electroluminescent device, comprising an arylamine derivative for an organic electroluminescent device having an asymmetric structure according to claim 1 or 5.
11. The organic thin film material for an organic electroluminescent device according to claim 10, wherein the organic thin film material is a light emitting material or a dopant material.
An organic electroluminescence device comprising a cathode, a cathode, and a plurality of organic thin film layers disposed between the anode and the cathode,
Wherein at least one of the plurality of organic thin film layers contains an arylamine derivative for an organic electroluminescence device having an asymmetric structure according to claim 1 or claim 5.
14. The organic electroluminescence device according to claim 12, wherein the organic thin film layer comprises at least one selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and an electron transport layer.
The organic electroluminescent device according to claim 12, wherein the organic thin film layer is a light emitting layer.
The organic electroluminescence device according to claim 12, wherein the organic thin film layer contains a host compound and a dopant compound.

Images