KR20150004214A - Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device - Google Patents

Abstract

In the present invention, provided are a novel aromatic amine compound with outstanding light-emitting efficiency and thermal stability, a manufacturing method thereof and an organic electron device including the novel aromatic amine compound. In the present invention, the novel aromatic amine derivative has outstanding thermal stability and is used in hole injection materials, hole transport materials, light-emitting materials and electron transport materials. In the present invention, the novel aromatic amine compound denoted by chemical formula 1 has different or the same Ar1 to Ar4 in which the Ar1 and an Ar2 can form unsubstituted or substituted cyclic by fusing with each other.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting material for an organic electroluminescent device, an organic electroluminescent device using the same, and a material for an organic electroluminescent device,

The present invention relates to a novel aromatic amine compound, a method for producing the same, and an organic electronic device using the same. More specifically, the present invention relates to a novel aromatic amine compound, A novel aromatic amine derivative having excellent thermal stability, a process for producing the same, and an organic electronic device including the derivative.

In general, organic light emitting diodes (OLEDs) are composed of a cathode (eg, aluminum or lithium aluminum), a cathode (eg, ITO), and an organic layer interposed between the cathode and anode. (EL), an electron transport layer (ETL), an electron transport layer (EIL), a hole injection layer (HIL), a hole transport layer (HTL) LiAl or the like, and one or two organic layers may be omitted if necessary. When an electric field is applied between the electrodes, electrons are injected into the cathode and holes are injected into the anode. Further, the electrons recombine with the holes in the light emitting layer to generate an excited state, and emit energy as light when the excited state returns to the ground state.

Such a light emitting material is largely divided into fluorescence and phosphorescence. The method of forming a light emitting layer includes a method of doping a fluorescent host (pure organic material) with phosphorescence (organic metal), a method of doping a fluorescent dopant (organic material including nitrogen etc.) And a method of implementing a long wavelength using a dopant (DCM, Rubrene, DCJTB, etc.) on a light emitting body. Such doping is intended to improve the emission wavelength, efficiency, driving voltage, lifetime, and the like.

In general, HIL has 2-TNATA (4,4 ', 4 "-tris- (N- (naphthylen-2-yl) , 4 '' - Tris (N-3-methylphenyl-N-phenylamino) triphenylamine), TCTA (4,4 ', 4-tris (triphenylamine) ) And the like are used, and HTL is a-NPD (4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), OA-3 (N1, N1- ) -N4- (4- (dibiphenyl-4-ylamino) phenyl) -N4-phenylbenzene-1,4-diamine), Spiro-TPD (N2, N2, N2 ', N2', N7, N7, N7 ' -octaphenyl-9,9'-spirobi [fluorene] -2,2 ', 7,7'-tetraamine).

The ETL can also be selected from the group consisting of Alq3 (Tris (8-hydroxyquinolinato) aluminum), L01 (9,10-di (quinolin-2-yl) anthracene), TmPyPB (1,3,5- ) benzene) are used as the common layer of the OLED. However, materials such as a-NPD or TmPyPb exhibit low thermal stability (Tg <100 ° C. Tg; Glass Temperature) and are not used in mass production. In mass production, materials with high thermal stability (Tg> 130 ° C) are required to affect the lifetime.

The material for forming the light emitting layer may be selected from the group consisting of benzene, naphthalene, fluorene, spiroprolene, anthracene, pyrene and carbazole and a ligand such as phenyl, biphenyl, naphthalene and heterocycle and ortho, Cyanide, fluorine, methyl, trimethyl, and the like.

For example, in the case of blue, there is a compound such as a, b-ADN, b, b-MADN and BD1 in the above compound and green is represented by Indeno [1,2,3- cd] perylene, 5,12-diphenyltetracene and ATCDA Structures can be used, and red is Sony's BSN, Kodak's DCM2, and Idemitsu's PI.

As the screen of the display is enlarged in the direction of the enlargement of the display, more delicate and sharper materials are required for the OLED. Among them, blue is the biggest problem in the case of the problem and the light emitting material to be solved. High-performance light emitting materials are required in the current blue (> 470 nm) to blue (<460 nm) directions. In addition to the chromaticity coordinates of the emission wavelength, a high glass transition temperature, which is a high luminous efficiency at a low driving voltage of the device and a chemical structural thermal stability of the material, is required. In addition, common layers (HIL, HTL, ETL, etc.) are required to have materials that are excellent in thermal stability and lifetime, have high hole or electron mobility, and can improve device efficiency.

Prior art of the Republic of Korea for aromatic amine compounds is Pyrene, 10-2007-7005909, 10-2005-7017372, 10-2008-0123423, etc., and for Carbazole, 10-2005 -0039461, 10-2005-0042359, 10-2006-0132827, 10-2009-0129799, etc., and the ring-forming compounds are 10-2013-0052663, 10-2013-0045570, 10-2013-0018875, 10- 2013-0009392. However, for the technological development of organic electroluminescence, light emitting materials are required to have emission wavelength, high luminous efficiency and thermal stability, and in the case of a common layer, there is still a need to develop a compound having high hole / electron mobility .

The present invention relates to an aromatic compound having a cyclic structure and exhibits excellent heat stability and exhibits excellent luminescence efficiency through introduction of a core or a ligand excellent in electron density, It is intended to provide a novel aromatic amine derivative which improves the performance of a device through introduction of a core or a ligand.

The present invention also provides an organic electrical device comprising the novel aromatic amine derivative.

The present inventors provide aromatic compounds forming a ring and a novel aromatic amine derivative represented by the following formula (1) for improving the performance of the device:

In Formula 1,

Z is in each case the same or different and is N (nitrogen), O (oxygen), S (sulfur), and when Z is N, L ₁ and L ₂ are integers of 1 and O Sulfur), L ₁ and L ₂ are integers of zero. L ₃ is an integer of 0 or 1.

Ar ₁ to Ar ₄ may be the same or different and each represents a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number A substituted or unsubstituted aralkylthiol group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 8 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms An arylthiol group having 6 to 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group, and Ar ₁ and Ar ₂ may be fused to each other to form a substituted or unsubstituted ring.

R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms group, or are substituted or unsubstituted, can be carbon atoms selected 6-50 aryl thiol, a group non-substituted or carbon atoms substituted with a 6-50 arylamine group, a silyl group, a phosphine oxide, R ₁ to R ₃ or Ar ₁ to Ar ₄ may be fused with each other to form a substituted or unsubstituted ring.

According to another aspect of the present invention, there is provided an organic electronic device including the novel aromatic amine derivative of Formula 1.

The novel aromatic amine derivatives according to the present invention can form various cores of Ar ₁ to Ar ₄ and can improve performance and functionality by improving electron density. Further, it is possible to control fine wavelengths of light emission, improve performance, and improve functionality by adjusting the molecular weight of the ligands of R ₁ to R ₃ and the kind of the ligand.

In addition, the organic electronic device using the novel aromatic amine derivative according to the present invention has high luminance, excellent heat resistance, long life and high efficiency.

Hereinafter, the present invention will be described in detail. The following detailed description is only illustrative of the present invention, and thus the present invention is not limited thereto.

According to one aspect of the present invention, there is provided a novel aromatic amine derivative represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

Z is in each case the same or different and is N (nitrogen), O (oxygen), S (sulfur), and when Z is N, L ₁ and L ₂ are integers of 1 and O Sulfur), L ₁ and L ₂ are integers of zero. L ₃ is an integer of 0 or 1.

Ar ₁ to Ar ₄ may be the same or different and each represents a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number A substituted or unsubstituted aralkylthiol group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 8 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms An arylthiol group having 6 to 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group, and Ar ₁ and Ar ₂ may be fused to each other to form a substituted or unsubstituted ring.

R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms group, or are substituted or unsubstituted, can be carbon atoms selected 6-50 aryl thiol, a group non-substituted or carbon atoms substituted with a 6-50 arylamine group, a silyl group, a phosphine oxide, R ₁ to R ₃ or Ar ₁ to Ar ₄ may be fused with each other to form a substituted or unsubstituted ring.

In Formula 1, each of R ₁ to R ₃ may independently be selected from the following formulas, but is not limited thereto.

X and Y may be the same or different from each other and each represent a hydrogen atom, a cyan atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, An aralkyl group having 7 to 40 carbon atoms in the ring, a substituted or unsubstituted aralkyloxy group having 7 to 40 carbon atoms, a substituted or unsubstituted aralkylthio group having 7 to 40 carbon atoms, a substituted or unsubstituted carbon atom number A substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 50 carbon atoms , A substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms, an amino group, a cyano group, a silyl group, and a phosphine oxide group.

The definition of terms used in this specification will be described in detail as follows.

, 시아노기, 치환 또는 비치환된 아미노기(-NH₂, -NH(R), -N(R')(R''), R'과 R"은 서로 독립적으로 탄소수 1 내지 10의 알킬기임), 아미디노기, 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알케닐기, C1-C20의 알키닐기, C1-C20의 헤테로알킬기, C6-C20의 아릴기, C6-C20의 아릴알킬기, C6-C20의 헤테로아릴기, 또는 C6-C20의 헤테로아릴알킬기로 치환될 수 있다. 이러한 알킬기의 예로서 메틸, 에틸, 프로필, 2-프로필, n-부틸, 이소-부틸, tert-부틸, 펜틸, 헥실, 도데실, 플루오로메틸, 디플루오로메틸, 트리플루오로메틸, 클로로메틸, 디클로로메틸, 트리클로로메틸, 요오도메틸, 브로모메틸 등을 들 수 있다. "Alkyl group" means a straight or branched saturated monovalent hydrocarbon portion of a carbon atom. The at least one hydrogen atom contained in the alkyl group may be substituted with a halogen atom, a silyl group, a phosphine oxide group, a hydroxyl group, -SH, a nitro group,

, A cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms) A C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C1-C20 alkenyl group, a C1-C20 alkynyl group, a C1-C20 alkynyl group, An aryl group of C6-C20, an arylalkyl group of C6-C20, a heteroaryl group of C6-C20, or a heteroarylalkyl group of C6-C20. Examples of such alkyl groups include methyl, ethyl, Propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, , Bromomethyl and the like.

The "aryl group" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety, and at least one hydrogen atom of the aryl group may be substituted with the same substituent as the alkyl group. The aromatic moiety of the aryl group contains only carbon atoms. Examples of aryl groups include phenyl, naphthalenyl and fluorenyl.

 Means a monovalent monocyclic or bicyclic aromatic radical having 1, 2 or 3 heteroatoms selected from N, O or S and the remaining ring atoms C, The term also refers to monovalent monocyclic or bicyclic aromatic radicals in which the heteroatoms in the ring are oxidized or tanned to form, for example, N-oxides or quaternary salts. Representative examples include thienyl, benzothienyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, quinoxalinyl, imidazolyl, furanyl, benzofuranyl, thiazolyl, isoxazoline, Benzimidazolyl, benzimidazolyl, benzimidazolyl, triazolyl, pyrazolyl, pyrrolyl, indolyl, 2-pyridonyl, N-alkyl-2-pyridonyl, pyridazinonyl, pyridazinonyl, , Oxazolonyl, and the corresponding N-oxides (e.g., pyridyl N-oxide, quinolinyl N-oxide), quaternary salts thereof, and the like. At least one hydrogen atom in the heterocyclic group may be substituted with the same substituent as the alkyl group.

"Amine group substituted with an aryl group" One or more hydrogen atoms of the amino group are substituted with an aryl group, and at least one hydrogen atom of the aryl group can be substituted with the same substituent as the aryl group.

"Aralkyl" or "arylalkyl" means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and at least one hydrogen atom of the aralkyl group may be substituted with the same substituent as the alkyl group. Examples thereof include benzyl, benzhydryl and trityl.

The terms "alkoxy group "," aralkyloxy group ", and "aryloxy group" refer to a form in which oxygen is further contained at the linkage bonding sites of the aforementioned "alkyl group", "aralkyl group" Alkylthio group "and" arylthio group "refer to a form in which sulfur is further contained at the linkage bonding sites of the" aralkyl group "and the" aryl group ".

 "Bond" refers to a moiety attached only to a simple bond without any substituent attached thereto.

Wherein R ₁ to R ₃ may be substituted with at least one more than, independently from each other are selected from the other substituents of the hydrogen attached to the these of the carbon, as described above, and examples thereof include an amino group, a cyano group, a silyl group, a hydroxyl group, or There may be, but is not limited to, a phosphine oxide group.

Ar ₁ to Ar ₄ in the general formula (1) can be represented by the following general formulas (2-1) and (2-2)

[Formula 2-1]

[Formula 2-2]

2-1 and 2-2

Z is in each case the same or different and is N (nitrogen), O (oxygen), S (sulfur), and when Z is N, L ₁ and L ₂ are integers of 1 and O Sulfur), L ₁ and L ₂ are integers of zero.

R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms An arylthiol group having 6 to 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.

R ' ₁ to R' ₈ in each case are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 1 to 30 carbon atoms A substituted or unsubstituted alkylthiol group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon An alkenyloxy thiol group having 2 to 30 atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted 7 carbon atoms A substituted or unsubstituted aralkylthiol group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms , Or a substituted or unsubstituted arylthio group having 6 to 50 carbon atoms An unsubstituted or substituted aryl group having 6 to 50 carbon atoms, a silyl group, or a phosphine oxide group, and R ₁ to R ₃ or R ' ₁ to R' _{8 may have} at least two adjacent May be fused to each other to form a substituted or unsubstituted ring.

More specific embodiments of Formula 1 may be represented by the following Formulas 3-1 to 3-66:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Formula 3-11]

(3-12)

[Chemical Formula 3-13]

[Chemical Formula 3-14]

[Chemical Formula 3-15]

[Chemical Formula 3-16]

[Formula 3-17]

[Chemical Formula 3-18]

[Chemical Formula 3-19]

[Formula 3-20]

[Chemical Formula 3-21]

[Chemical Formula 3-22]

[Chemical Formula 3-23]

[Chemical Formula 3-24]

[Formula 3-25]

[Chemical Formula 3-26]

[Chemical Formula 3-27]

[Chemical Formula 3-28]

[Chemical Formula 3-29]

[Chemical Formula 3-30]

[Chemical Formula 3-31]

(3-32)

[Chemical Formula 3-33]

[Chemical Formula 3-34]

[Formula 3-35]

[Chemical Formula 3-36]

[Chemical Formula 3-37]

[Chemical Formula 3-38]

[Formula 3-39]

[Formula 3-40]

[Chemical Formula 3-41]

[Chemical Formula 3-42]

[Chemical Formula 3-43]

[Chemical Formula 3-44]

[Chemical Formula 3-45]

[Chemical Formula 3-46]

[Chemical Formula 3-47]

[Chemical Formula 3-48]

[Chemical Formula 3-49]

[Formula 3-50]

[Formula 3-51]

[Formula 3-52]

[Formula 3-53]

[Chemical Formula 3-54]

[Chemical Formula 3-55]

[Chemical Formula 3-56]

[Chemical Formula 3-57]

[Chemical Formula 3-58]

[Chemical Formula 3-59]

[Formula 3-60]

[Formula 3-61]

[Formula 3-62]

[Formula 3-63]

[Chemical Formula 3-64]

[Formula 3-65]

[Formula 3-66]

In the above formulas (3-1) to (3-66)

R ' ₁ to R' ₈ or Q ₁ and Q ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon atom A substituted or unsubstituted alkylthiol group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group having 2 to 50 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, A substituted or unsubstituted alkenyloxy thiol group having 2 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, An aralkylthiol group having 7 to 50 carbon atoms in the ring, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, An aryloxy group having 1 to 50 carbon atoms, or a substituted or unsubstituted carbon atom number An arylthiol group having 6 to 50 carbon atoms, and a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms, and Q ₁ and Q ₂ may be fused to each other to form a substituted or unsubstituted ring.

Y ₁ to Y ₃ may be the same or different and each represents a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms Or an arylthiol group having 6 to 50 carbon atoms, which may be substituted or unsubstituted, and may be selected from a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms.

R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms Or an arylthiol group having 6 to 50 carbon atoms, which may be substituted or unsubstituted, and may be selected from a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms.

According to another aspect of the present invention there is provided a process for the preparation of the novel aromatic amine (s), including an amination reaction, a substitution reaction, an ether compound or a sulfuration compound by debenzoylation, A process for preparing a derivative is provided.

One aspect of the process for producing the novel aromatic amine derivative is as follows.

5 (or b-2, c-3, d-2) is synthesized by using (I) amination, substitution reaction or ether compound or sulfuration compound synthesis method as shown in Scheme 1 (II) a step of removing benzoyl as in a-6 (or b-3, c-4, d-3), and (III) .

[Reaction Scheme 1]

In the above formula (1), Z, R ₁ to R _3, and Ar ₁ to Ar ₄ and L ₁ to L ₃ are as defined above.

According to an aspect of the present invention, there is provided an organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the electrodes, wherein at least one layer of the organic material layer is a novel aromatic amine derivative An organic electroluminescent device is provided.

The novel aromatic amine derivative may be included in the organic material layer in the form of a single material or a mixture of different materials.

The organic material layer may include a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer, And a functional layer. At least one of the hole injecting layer, the hole transporting layer, and the functional layer having both the hole injecting function and the hole transporting function may be a charge injecting material, a hole transporting material, a hole injecting and transporting material, Product material.

In the present specification, the term "organic layer" refers to all layers interposed between the first electrode and the second electrode in the organic electronic device.

For example, the organic layer may include a light emitting layer, and the light emitting layer may include at least one of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant. Wherein the light emitting layer contains the novel aromatic amine derivative and i) the fluorescent host is the novel aromatic amine derivative, or ii) the fluorescent dopant is the novel aromatic amine derivative, or iii) the fluorescent host and the fluorescent plate Each of which may be the novel aromatic amine derivative.

The light emitting layer may be a red, green or blue light emitting layer. For example, the light emitting layer may be a blue light emitting layer. At this time, the novel aromatic amine derivative is used as a blue host and / or a blue dopant, thereby providing an organic electronic device having high efficiency, high luminance, high color purity, and long life.

Further, the organic material layer may include an electron transporting layer, and the novel aromatic amine derivative may be included in the electron transporting layer. Here, the electron transporting layer may further include a metal-containing compound in addition to the novel aromatic amine derivative.

Wherein the organic material layer includes both a light emitting layer and an electron transporting layer and the novel aromatic amine derivative (the novel aromatic amine derivative contained in the light emitting layer and the electron transporting layer may be the same or different from each other) in each of the light emitting layer and the electron transporting layer .

The organic electronic device can be produced by a conventional method and materials for producing an organic electronic device, except that a novel aromatic amine derivative represented by the general formula (1) is used.

As an embodiment of the present invention, the organic electronic device may be an organic light emitting diode (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoconductor (OPC) .

The organic light emitting device may be formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. The organic layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. The organic material layer may be formed using a variety of polymer materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, .

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used. The compound according to the present invention can act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an OLED for illumination, a flexible OLED, an organophotoreceptor, an organic transistor and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easy understanding of the present invention, and the present invention is not limited thereto.

In addition, it is understood that the compound in which the preparation method is not specifically disclosed in each of the examples of the present invention, may be prepared by a method customary in the art or by referring to the preparation method described in other examples.

&Lt; Preparation of intermediate &

Intermediate (1). Preparation of N, N-bis (3-bromophenyl) benzamide

(34 mmol) benzamide, 10.9 g (35 mmol) of 1,3-dibromobenzene, 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in a xylene solvent, For 3 hours. The temperature was lowered to room temperature, and 10.9 g (35 mmol) of 1,3-dibromobenzene was dissolved in 100 ml of a xylene solvent, and the mixture was reacted at 180 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 300 ml of toluene was added thereto, and the mixture was filtered through suction filtration, passed through a silica gel column, concentrated and washed with an ethyl acetate / methanol mixed solvent to obtain 73.7% of a solid compound (10.7 g).

Intermediate (1-1).

The following compounds of the following Table 1 were obtained by the method for producing the intermediates (1-2 to 1-13)

Starting material Product material yield(%) Intermediate
1-2

68% Intermediate
1-3

70% Intermediate
1-4

72% Intermediate
1-5

69% Intermediate
1-6

67% Intermediate
1-7

68% Intermediate
1-8

71% Intermediate
1-9

75% Intermediate
1-10

68% Intermediate
1-11

65% Intermediate
1-12

67% Intermediate
1-13

72%

* Intermediate (2-1). Preparation of N, N-bis (4-benzamidophenyl) benzamide

N, N-bis (4-bromophenyl) benzamide, 0.54 g (8.5 mmol) of copper and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in a xylene solvent , And reacted at 180 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and 200 ml of toluene was added thereto. The mixture was filtered through suction filtration, passed through a silica gel column, concentrated, and washed with a mixed solvent of ethyl acetate / methanol to obtain 84.2 g of a solid compound (15.2 g).

Intermediate (2-2). Preparation of intermediate

The following compounds of the following Table 2 were obtained by the method for producing the intermediate (2-1)

Starting material Product material yield(%) Intermediate
2-2

86% Intermediate
2-3

83% Intermediate
2-4

84%

* Intermediate (2-5). Preparation of N, N-bis (7-aminonaphthalen-2-yl) benzamide

Bu, 6.7 g (7 mmol) of NaO-t-Bu, N, N-bis (trimethylsilyl) borate (0.025 mmol) 2.7 g (5 mmol) of 7-bromonaphthalen-2-yl) benzamide and 50 ml of ammonia (a solution of 0.5 mol of 1,4-dioxine) were dissolved in toluene solvent and reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of toluene was added, and the mixture was separated by suction filtration and separated by a silica gel column (hexane: ethyl acetate = 3: 1) and concentrated to obtain 84% of a solid compound (1.7 g).

Intermediates (2-6-2-13). Preparation of intermediates

The following compounds of the following Table 3 were obtained by the method for producing the intermediate (2-5)

Starting material Product material yield(%) Intermediate
2-6

82% Intermediate
2-7

79% Intermediate
2-8

85% Intermediate
2-9

83% Intermediate
2-10

79% Intermediate
2-11

78% Intermediate
2-12

76% Intermediate
2-13

81%

* Intermediate (3-1). Preparation of A-1

N, N-bis (3-bromophenyl) benzamide, 3.8 g (35 mmol) of benzene-1,3-diamine and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in DMF solvent in a nitrogen atmosphere, The reaction was carried out at 100 ° C for 2 hours. After completion of the reaction, the reaction mixture was filtered by suction filtration, concentrated, and then recrystallized (0.6 g) to obtain 68%.

* Intermediate (3-2). Preparation of A-2

A mixture of 12.8 g (34 mmol) of A-1 intermediate, 15.3 g (74 mmol) of 4-bromonaphthalene, 0.6 g (10 mmol) of copper and 6 g (44 mmol) of dried potassium carbonate, 0.5 g , 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 55% of A-2 (11.8 g) intermediate.

* Intermediate (3-3). Preparation of A-3

N-bis (3-bromophenyl) benzamide, 9.0 g (35 mmol) of 1,3-dihydroindolo [2,3-b] carbazole and 7.8 g (81.6 mmol) of sodium- -Butoxide, o-xylene (300 ml) was added, and the mixture was refluxed for 2 hours. After the temperature was lowered to room temperature, 0.9 ml of tri-tert-butylphosphine solution (0.012 g) and bis-acetylpalladium (II) were added, and the mixture was refluxed for another 20 hours. When the reaction was completed, the solvent was vacuum-dried, and THF 200 m was added, followed by filtration, followed by concentration, and silica gel chromatography (toluene / hexane = 1/6) was conducted to obtain 54% of A-3 (9.6 g)

* Intermediate (3-4). Preparation of A-4

5-tert-butylbenzene-1,3-diamine, 5.7 g (35 mmol) of potassium carbonate were added to a solution of 18.5 g (34 mmol) N, N-bis (3-bromo- 50.6 mmol) was dissolved in a DMF solvent, and the mixture was reacted at 100 DEG C for 2 hours. After completion of the reaction, the reaction product was separated by suction filtration, concentrated, and then recrystallized to obtain 58% of A-4 (10.7 g) intermediate.

Intermediates (3-5-3-18). Preparation of intermediates

The following compounds of the following Table 4 were obtained by the method for producing the intermediate (3-4):

Starting material Product material yield(%) Intermediate
3-5

53% Intermediate
3-6

55% Intermediate
3-7

52% Intermediate
3-8

55% Intermediate
3-9

49% Intermediate
3-10

51% Intermediate
3-11

53% Intermediate
3-12

51% Intermediate
3-13

53% Intermediate
3-14

49% Intermediate
3-15

53% Intermediate
3-16

48% Intermediate
3-17

51% Intermediate
3-18

53%

Intermediates (3-19-3-32). Preparation of intermediates

The following compounds of the following Table 5 were obtained by the method for producing the intermediate (3-5):

Starting material Product material yield(%) Intermediate
3-19

52% Intermediate
3-20

54% Intermediate
3-21

51% Intermediate
3-22

50% Intermediate
3-23

48% Intermediate
3-24

49% Intermediate
3-25

46% Intermediate
3-26

51% Intermediate
3-27

50 Intermediate
3-28

52% Intermediate
3-29

51% Intermediate
3-30

55% Intermediate
3-31

48% Intermediate
3-32

53%

* Intermediate (3-33). Preparation of C-1

N, N-bis (7-aminonaphthalen-2-yl) benzamide, 10 g (35 mmol) of 2,7-dibromonaphthalene and 7 g (50.6 mmol) of dried potassium carbonate were dissolved in DMF , And reacted at 100 ° C for 2 hours. After completion of the reaction, the mixture was separated by suction filtration, concentrated, and then recrystallized to obtain (10.4 g) as 58%.

* Intermediate (3-34 ~ 3-44). Preparation of intermediates

The following compounds of the following Table 6 were obtained by the method for producing the intermediate (3-33)

Starting material Product material yield(%) Intermediate
3-34

55% Intermediate
3-35

53% Intermediate
3-36

51% Intermediate
3-37

54% Intermediate
3-38

49% Intermediate
3-39

45% Intermediate
3-40

49% Intermediate
3-41

51% Intermediate
3-42

53% Intermediate
3-43

50% Intermediate
3-44

46%

* Intermediate (3-45 ~ 3-46). Preparation of intermediates

The following compounds of the following Table 7 were obtained by the method for producing the intermediate (3-1)

Starting material Product material yield(%) Intermediate
3-45

55% Intermediate
3-46

53%

* Intermediate (3-47 ~ 3-74). Preparation of intermediates

The following compounds of the following Table 8 were obtained by the method for producing the intermediate (3-5):

Starting material Product material yield(%) Intermediate
3-47 Intermediate 2-3

49% Intermediate
3-48 Intermediate 2-3

53% Intermediate
3-49 Intermediate 2-3

55% Intermediate
3-50 Intermediate 2-3

52% Intermediate
3-51 Intermediate 2-3

49% Intermediate
3-52 Intermediate 2-3

51% Intermediate
3-53 Intermediate 2-3

48% Intermediate
3-54 Intermediate 2-3

53% Intermediate
3-55 Intermediate 2-3

55% Intermediate
3-56 Intermediate 2-3

54% Intermediate
3-57 Intermediate 2-3

52% Intermediate
3-58 Intermediate 2-3

55% Intermediate
3-59 Intermediate 2-3

53% Intermediate
3-60 Intermediate 2-3

51% Intermediate
3-61 Intermediate 2-4

55% Intermediate
3-62 Intermediate 2-4

49% Intermediate
3-63 Intermediate 2-4

54% Intermediate
3-64 Intermediate 2-4

52% Intermediate
3-65 Intermediate 2-4

45% Intermediate
3-66 Intermediate 2-4

49% Intermediate
3-67 Intermediate 2-4

48% Intermediate
3-68 Intermediate 2-4

52% Intermediate
3-69 Intermediate 2-4

55% Intermediate
3-70 Intermediate 2-4

57% Intermediate
3-71 Intermediate 2-4

49% Intermediate
3-72 Intermediate 2-4

51% Intermediate
3-73 Intermediate 2-4

53% Intermediate
3-74 Intermediate 2-4

51%

* Intermediate (3-75). Preparation of F-1

3-bromo-5-tert-butylphenyl) benzamide, 3.3 g (30 mmol) of 1,3-benzenediol and 6 g (44 mmol) of dried potassium carbonate in 16.3 g (30 mmol) , 200 ml of DMF was added, and the mixture was reacted at 70 캜 for 48 hours. After filtration, 120 ml of cyclohexane and hexane were added and precipitated. The precipitate was filtered and dried. The residue was subjected to silica gel chromatography to obtain 73% of the F-1 (10.8 g) intermediate.

* Intermediate (3-76). Production of G-1

69% of G-1 (8.5 g) intermediate was obtained as a preparation method for the intermediate (3-75).

&Lt; Preparation of Example &

[Example 1] A-1 Production

6.8 g (18 mmol) of Intermediate A-1 was dissolved in a xylene solvent, and then 2.2 g (40 mmol) of potassium hydroxide and 40 ml of 2-propanol were added and reacted at 70 ° C. for 1 hour. After 2-propanol was removed, 50 ml of toluene was added and the mixture was refluxed for 1 hour. After filtration at 50 캜, the filtrate was dried to obtain 93% of solid compound (A-1 '4.6 g).

* Example 1. A-1 Preparation of

A mixture of 8.2 g (30 mmol) of A-1, 19.7 g (95 mmol) of 1-bromonaphthalene, 0.6 g (10 mmol) of copper and 6 g (44 mmol) of dried potassium carbonate and 0.5 g of sodium bisulfate After adding 10 ml of dodecane and 30 ml of xylene, the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 53% of A-1 (10.4 g)

[Example 2] Preparation of A-2?

12.6 g (20 mmol) of A-2 'prepared in Example A-1', 4.6 g (22 mmol) of 2-bromonaphthalene and 0.6 g (10 mmol) of copper and 6 g mmol) and 0.5 g of sodium sulfate were added thereto. Then, 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain A-2 (7.2 g) and Example 2 at 55%.

[Example 3] A-3? Preparation

8.4 g (20 mmol) of A-3 'prepared in Example A-1', 7.1 g (22 mmol) of 4-bromo-N, N-diphenylaniline, 0.6 g (10 mmol) After adding 6 g (44 mmol) of potassium carbonate and 0.5 g of sodium bisulfate, 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain A-3 (6.8 g) and 51% of Example 3.

[Example 4] A-4 Manufacture

A mixture of 8.8 g (20 mmol) of A-4 'prepared in Example A-1', 14.9 g (95 mmol) of bromobenzene, 0.6 g (10 mmol) of copper and 6 g ) And 0.5 g of sodium sulfate were added thereto. Then, 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain A-4 (6.8 g) and Example 4 at 53%.

Preparation of [Examples 5 to 32]

The following compounds of the following Table 9 were obtained by the production method of Example 4:

Starting material Intermediates / Additives Product material yield(%) room
city
Yes
5 Intermediate
3-5

/ 1-bromo-4-methoxybenzene

/ 1-bromo-4-methoxybenzene

50% room
city
Yes
6 Intermediate
3-6

/ 1-bromonaphthalene

53% room
city
Yes
7 Intermediate
3-7

/ 1-bromonaphthalene

51% room
city
Yes
8 Intermediate
3-8

/ 1-bromo-4-tert-butylbenzene

49% room
city
Yes
9 Intermediate
3-9

/ 4-bromobenzonitrile

47% room
city
Yes
10 Intermediate
3-10

/ 1-bromo-4-fluorobenzene

48% room
city
Yes
11 Intermediate
3-11

/ (4-bromophenyl) trimethylsilane

45% room
city
Yes
12 Intermediate
3-12

/ Phosphine oxide, (4-chlorophenyl) diphenyl-

47% room
city
Yes
13 Intermediate
3-13

/ 9-bromophenanthrene

54% room
city
Yes
14 Intermediate
3-14

/ 4-bromopyridine

56% room
city
Yes
15 Intermediate
3-15

/ 5-bromopyrimidine

54% room
city
Yes
16 Intermediate
3-16

/ bromobenzene

52% room
city
Yes
17 Intermediate
3-17

/ bromobenzene

51% room
city
Yes
18 Intermediate
3-18

/ bromobenzene

54% room
city
Yes
19 Intermediate
3-19

/ 4-bromobiphenyl

52% room
city
Yes
20 Intermediate
3-20

/ 4-bromobiphenyl

48% room
city
Yes
21 Intermediate
3-21

/ bromobenzene

51% room
city
Yes
22 Intermediate
3-22

/ bromobenzene

53% room
city
Yes
23 Intermediate
3-23

/ 4-bromobenzonitrile

48% room
city
Yes
24 Intermediate
3-24

/ 4-bromobenzonitrile

51% room
city
Yes
25 Intermediate
3-25

/ 4-bromobenzonitrile

49% room
city
Yes
26 Intermediate
3-26

/ 4-bromobenzonitrile

50% room
city
Yes
27 Intermediate
3-27

/ bromobenzene

54% room
city
Yes
28 Intermediate
3-28

/ 4-bromopyridine

52% room
city
Yes
29 Intermediate
3-29

/ 4-bromopyridine

49% room
city
Yes
30 Intermediate
3-30

/ 4-bromopyridine

51% room
city
Yes
31 Intermediate
3-31

/ 4-bromopyridine

53% room
city
Yes
32 Intermediate
3-32

/ bromobenzene

55%

Preparation of [Examples 33 to 44]

The following compounds of the following Table 10 were obtained by the preparation method of Example 1:

Starting material Intermediates / Additives Product material yield(%) room
city
Yes
33 Intermediate
3-33

/ bromobenzene

/ bromobenzene

57% room
city
Yes
34 Intermediate
3-34

/ 4-bromopyridine

53% room
city
Yes
35 Intermediate
3-35

/ bromobenzene

51% room
city
Yes
36 Intermediate
3-36

/ bromobenzene

53% room
city
Yes
37 Intermediate
3-37

/ bromobenzene

51% room
city
Yes
38 Intermediate
3-38

/ bromobenzene

48% room
city
Yes
39 Intermediate
3-39

/ bromobenzene

43% room
city
Yes
40 Intermediate
3-40

/ bromobenzene

46% room
city
Yes
41 Intermediate
3-41

/ bromobenzene

49% room
city
Yes
42 Intermediate
3-42

/ bromobenzene

53% room
city
Yes
43 Intermediate
3-43

/ bromobenzene

50% room
city
Yes
44 Intermediate
3-44

/ bromobenzene

46%

[Example 45] Production of D-1?

After adding 6.6 g (20 mmol) of D-1, 12.4 g (44 mmol) of 1-bromopyrene, 0.6 g (10 mmol) of copper and 6 g (44 mmol) of dried potassium carbonate and 0.5 g of sodium persulfate in a nitrogen atmosphere , 10 ml of dodecane and 30 ml of xylene solvent were added and refluxed at 220 캜 for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 54% of D-1? (7.9 g) of Example 45.

[Example 46] E-1? Preparation

E-5? 6.8 g) was obtained in the same manner as in Example 35, and 49% of Example 46 was obtained.

[Example 47] Production of D-2?

* Preparation of D-2 '

10 g (18 mmol) of Intermediate D-2 was dissolved in a xylene solvent, and then 2.2 g (40 mmol) of potassium hydroxide and 40 ml of 2-propanol were added and reacted at 70 ° C for 1 hour. After 2-propanol was removed, 50 ml of toluene was added and the mixture was refluxed for 1 hour. After filtration at 50 DEG C, the filtrate was dried to obtain 93% of a solid compound (D-2 '5.9 g) intermediate.

* Manufacture of D-2¨

Bromo-10-phenylanthracene, 0.6 g (10 mmol) of copper and 6 g (44 mmol) of dried potassium carbonate, 7 g (20 mmol) of sodium bisulfate , 10 ml of dodecane and 30 ml of xylene were added, and the mixture was refluxed at 220 ° C for 10 hours. 300 ml of toluene was slowly added dropwise thereto, and the mixture was cooled. After filtration at 80 DEG C, 120 ml of cyclohexane and hexane were added, precipitated, filtered and dried. The residue was subjected to silica gel chromatography (toluene / hexane = 1/6) to obtain 51% of D-2 (8.7 g) of Example 47.

Preparation of [Examples 48 to 74]

The following compounds of the following Table 11 were obtained by the preparation method of Example 47:

Starting material Intermediates / Additives Product material yield(%) room
city
Yes
48 Intermediate
3-48

/ 1-bromonaphthalene

/ 1-bromonaphthalene

53% room
city
Yes
49 Intermediate
3-49

/ 1-bromonaphthalene

54% room
city
Yes
50 Intermediate
3-50

/ 2-bromonaphthalene

53% room
city
Yes
51 Intermediate
3-51

/ 1-bromonaphthalene

46% room
city
Yes
52 Intermediate
3-52

/ 1-bromonaphthalene

51% room
city
Yes
53 Intermediate
3-53

/ 1-bromonaphthalene

47% room
city
Yes
54 Intermediate
3-54

/ 1-bromonaphthalene

49% room
city
Yes
55 Intermediate
3-55

/ 1-bromo-4-tert-butylbenzene

51% room
city
Yes
56 Intermediate
3-56

/ 4-bromopyridine

54% room
city
Yes
57 Intermediate
3-57

/ 4-bromopyridine

52% room
city
Yes
58 Intermediate
3-58

/ 4-bromopyridine

49% room
city
Yes
59 Intermediate
3-59

/ 4-bromopyridine

51% room
city
Yes
60 Intermediate
3-60

/ bromobenzene

53% room
city
Yes
61 Intermediate
3-61

/ 9-bromo-10-phenylanthracene

55% room
city
Yes
62 Intermediate
3-62

/ 1-bromonaphthalene

53% room
city
Yes
63 Intermediate
3-63

/ 1-bromonaphthalene

55% room
city
Yes
64 Intermediate
3-64

/ 2-bromonaphthalene

54% room
city
Yes
65 Intermediate
3-65

/ 1-bromonaphthalene

47% room
city
Yes
66 Intermediate
3-66

/ 1-bromonaphthalene

50% room
city
Yes
67 Intermediate
3-67

/ 1-bromonaphthalene

51% room
city
Yes
68 Intermediate
3-68

/ 1-bromonaphthalene

53% room
city
Yes
69 Intermediate
3-69

/ 1-bromo-4-tert-butylbenzene

49% room
city
Yes
70 Intermediate
3-70

/ 4-bromopyridine

55% room
city
Yes
71 Intermediate
3-71

/ 4-bromopyridine

51% room
city
Yes
72 Intermediate
3-72

/ 4-bromopyridine

53% room
city
Yes
73 Intermediate
3-73

/ 4-bromopyridine

51% room
city
Yes
74 Intermediate
3-74

/ bromobenzene

47%

Production of [Examples 75 to 76]

The following compounds of the following Table 12 were obtained by the production method of Example 2:

Starting material Intermediates / Additives Product material yield(%) room
city
Yes
75 Intermediate
3-75

/1-bromopyrene

/ 1-bromopyrene

48% room
city
Yes
76 Intermediate
3-76

/ 1-bromopyrene

46%

<Experimental Example>

The glass substrate coated with the ITO thin film with a thickness of 1500 Å was put into the second distilled water in which the detergent of the fisher was melted and was ultrasonically cleaned for 30 minutes. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent of isopropyl alcohol, acetone, and methanol, dried, and transferred to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator.

2-TNATA as a hole injection layer on the ITO transparent electrode prepared above, or the material of Example of Example as described in [Table 13] was vacuum deposited 500 Å, then a-NPD was used as a hole transporting layer, as after the vacuum deposition, and a host ADN, dopant TPPDA or Table 17 respectively laminated and doped, respectively 5% of the embodiment material as described in was vacuum deposited to a thickness of 300Å, the hole blocking layer and the hole transport layer Alq ₃ Or the material of Example of the present invention was vacuum deposited to a thickness of 400 Å as described in [Table 13], and LiF 5 Å and Al (aluminum) 2000 Å were sequentially deposited to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of LiF was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

The electroluminescent characteristics of the organic light-emitting device prepared above are shown in Table 13 below.

Common layer The light- Current density
(mA / cm ² ) color efficiency
(cd / A) life span
(hrs) Comparative Experimental Example General material TPPDA 20 Light blue 3.8 3,500 The light-
Dopant
Experimental Example Example 13 20 blue 7.8 8,700 Example 33 20 blue 5.1 8,500 Example 44 20 blue 4.6 8,300 Example 45 20 blue 8.5 9,500 HIL
Comparative Experimental Example Example 1 TPPDA 20 Light blue 5.4 7,200 Example 2 20 Light blue 5.8 7,500 Example 3 20 Light blue 4.7 6,800 Example 8 20 Light blue 6.2 7,800 HTL
Comparative Experimental Example Example 6 20 Light blue 5.7 7,100 Example 7 20 Light blue 5.9 7,400 Example 48 20 Light blue 5.2 6,800 Example 49 20 Light blue 5.3 6,900 ETL
Comparative Experimental Example Example 15 20 Light blue 6.1 7,900 Example 29 20 Light blue 5.7 7,600 Example 57 20 Light blue 5.4 7,300

From the results of the above Table 13, it was confirmed that the novel aromatic amine derivative according to the present invention has improved luminescence efficiency and lifetime characteristics in the role of a dopant of a luminescent material and improved luminescent efficiency and lifetime characteristics in the role of a common layer .

The organic light emitting device using the novel aromatic amine derivative of the present invention has been improved in luminous efficiency and lifetime. Therefore, it is industrially useful as an OLED having high practicality.

INDUSTRIAL APPLICABILITY The organic light emitting device of the present invention can be suitably used for a light source such as a flat panel display, a planar light emitting body, a light emitting body of a surface emitting OLED for illumination, a flexible light emitting body, a copying machine, a printer, an LCD backlight or a meter, a display plate,

Claims (9)

A novel aromatic amine compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
Z is in each case the same or different and is N (nitrogen), O (oxygen), S (sulfur), and when Z is N, L ₁ and L ₂ are integers of 1 and O Sulfur), L ₁ and L ₂ are integers of zero. L ₃ is an integer of 0 or 1.
Ar ₁ to Ar ₄ may be the same or different and each represents a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number A substituted or unsubstituted aralkylthiol group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 8 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms An arylthiol group having 6 to 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group, and Ar ₁ and Ar ₂ may be fused to each other to form a substituted or unsubstituted ring.
R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms group, or are substituted or unsubstituted, can be carbon atoms selected 6-50 aryl thiol, a group non-substituted or carbon atoms substituted with a 6-50 arylamine group, a silyl group, a phosphine oxide, R ₁ to R ₃ or Ar ₁ to Ar ₄ may be fused with each other to form a substituted or unsubstituted ring.
The method according to claim 1,
Wherein Ar ₁ to Ar ₄ in the general formula (1) are represented by any one of the following general formulas (2-1) and (2-2):
[Formula 2-1]

[Formula 2-2]

2-1 and 2-2
Z is in each case the same or different and is N (nitrogen), O (oxygen), S (sulfur), and when Z is N, L ₁ and L ₂ are integers of 1 and O Sulfur), L ₁ and L ₂ are integers of zero.
R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms An arylthiol group having 6 to 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a silyl group, and a phosphine oxide group.
R ' ₁ to R' ₈ in each case are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 1 to 30 carbon atoms A substituted or unsubstituted alkylthiol group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon An alkenyloxy thiol group having 2 to 30 atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted 7 carbon atoms A substituted or unsubstituted aralkylthiol group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms , Or a substituted or unsubstituted arylthio group having 6 to 50 carbon atoms An unsubstituted or substituted aryl group having 6 to 50 carbon atoms, a silyl group, or a phosphine oxide group, and R ₁ to R ₃ or R ' ₁ to R' _{8 may have} at least two adjacent May be fused to each other to form a substituted or unsubstituted ring. The method according to claim 1,
Wherein Ar ₁ to Ar ₄ in Formula 1 are represented by any one of the following Formulas 3-1 to 3-66:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Formula 3-11]

(3-12)

[Chemical Formula 3-13]

[Chemical Formula 3-14]

[Chemical Formula 3-15]

[Chemical Formula 3-16]

[Formula 3-17]

[Chemical Formula 3-18]

[Chemical Formula 3-19]

[Formula 3-20]

[Chemical Formula 3-21]

[Chemical Formula 3-22]

[Chemical Formula 3-23]

[Chemical Formula 3-24]

[Formula 3-25]

[Chemical Formula 3-26]

[Chemical Formula 3-27]

[Chemical Formula 3-28]

[Chemical Formula 3-29]

[Chemical Formula 3-30]

[Chemical Formula 3-31]

(3-32)

[Chemical Formula 3-33]

[Chemical Formula 3-34]

[Formula 3-35]

[Chemical Formula 3-36]

[Chemical Formula 3-37]

[Chemical Formula 3-38]

[Formula 3-39]

[Formula 3-40]

[Chemical Formula 3-41]

[Chemical Formula 3-42]

[Chemical Formula 3-43]

[Chemical Formula 3-44]

[Chemical Formula 3-45]

[Chemical Formula 3-46]

[Chemical Formula 3-47]

[Chemical Formula 3-48]

[Chemical Formula 3-49]

[Formula 3-50]

[Formula 3-51]

[Formula 3-52]

[Formula 3-53]

[Chemical Formula 3-54]

[Chemical Formula 3-55]

[Chemical Formula 3-56]

[Chemical Formula 3-57]

[Chemical Formula 3-58]

[Chemical Formula 3-59]

[Formula 3-60]

[Formula 3-61]

[Formula 3-62]

[Formula 3-63]

[Chemical Formula 3-64]

[Formula 3-65]

[Formula 3-66]

In the above formulas (3-1) to (3-66)
R ' ₁ to R' ₈ or Q ₁ and Q ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon atom A substituted or unsubstituted alkylthiol group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group having 2 to 50 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, A substituted or unsubstituted alkenyloxy thiol group having 2 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, An aralkylthiol group having 7 to 50 carbon atoms in the ring, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, An aryloxy group having 1 to 50 carbon atoms, or a substituted or unsubstituted carbon atom number An arylthiol group having 6 to 50 carbon atoms, and a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms, and Q ₁ and Q ₂ may be fused to each other to form a substituted or unsubstituted ring.
Y ₁ to Y ₃ may be the same or different and each represents a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms Or an arylthiol group having 6 to 50 carbon atoms, which may be substituted or unsubstituted, and may be selected from a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms.
R ₁ to R _{3, which} may be the same or different from each other, are a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom number An aralkylthiol group having 7 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 50 carbon atoms Or an arylthiol group having 6 to 50 carbon atoms, which may be substituted or unsubstituted, and may be selected from a substituted or unsubstituted aminoaryl group having 6 to 50 carbon atoms. The method according to claim 1,
A novel aromatic amine compound, wherein R ₁ to R ₃ are selected from the following formulas:

X and Y may be the same or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted carbon atom An aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted amino group having 6 to 50 carbon atoms Lt; / RTI &gt; An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the electrodes,
Wherein at least one layer of the organic material layer comprises the novel aromatic amine compound according to any one of claims 1 to 4. 6. The method of claim 5,
The organic material layer may include a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer, And at least one of the functional layers. 6. The method of claim 5,
Wherein the organic electronic device is an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoconductor (OPC), or an organic transistor (OTFT). The method according to any one of claims 1 to 4, comprising the steps of an amination reaction, a substitution reaction, and an ether compound or a sulfuration compound by debenzoylation by displacement of hydrogen bromide &Lt; / RTI &gt; 9. The method of claim 8,
The preparation method is as shown in the following Reaction Scheme 1
(Or b-2, c-3, d-2) using (I) amination, substitution reaction and ether or sulfuration compound synthesis method, (II) (III) an amination reaction to obtain a compound of the formula (1), wherein the compound of the formula (1) is a compound of the formula &Lt; RTI ID = 0.0 &gt;

[Reaction Scheme 1]
In the above formula (1), Z, R ₁ to R _3, and Ar ₁ to Ar ₄ and L ₁ to L ₃ are as defined above.