KR20140128879A - Aromatic amine derivative and organic electroluminescent device comprising same - Google Patents

Abstract

The present invention is an organic light emitting compound characterized by an aromatic amine derivative represented by chemical formula A. The aromatic amine derivative has excellent light emitting properties such as brightness, luminous efficiency, etc. compared with that of a conventional light emitting material. Thus, an organic electroluminescent device including the same has excellent light emitting properties.

Description

TECHNICAL FIELD [0001] The present invention relates to an aromatic amine derivative and an organic electroluminescent device including the same. BACKGROUND ART [0002] AROMATIC AMINE DERIVATIVE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING SAME [0003]

The present invention relates to an aromatic amine derivative and an organic electroluminescent device including the aromatic amine derivative. The organic electroluminescent device including the aromatic amine derivative according to the present invention has excellent light emission characteristics such as brightness and luminous efficiency.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color.

Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

However, in order to sufficiently exhibit the excellent characteristics of the above-described organic light emitting device, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material and an electron injecting material, However, development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently achieved yet, and therefore development of a new material has been continuously required.

SUMMARY OF THE INVENTION The present invention provides a novel aromatic amine derivative and an organic electroluminescent device employing the aromatic amine derivative and having excellent light emission characteristics such as luminance and luminous efficiency.

In order to solve the above problems, the present invention provides an aromatic amine derivative represented by the following formula (A).

(A)

The present invention also provides an organic electroluminescent device having an anode, a cathode, and an organic material layer interposed between the anode and the cathode, the organic amine compound including an aromatic amine derivative represented by the above formula (A).

Specific substituents of the above-mentioned formula (A) will be described later.

The aromatic amine derivative compound according to the present invention has excellent quantum efficiency and has excellent luminescence characteristics such as brightness and luminescence efficiency as compared with the conventional luminescent material, so that the organic electroluminescent device including the same has excellent luminescent characteristics.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention is an organic luminescent compound which improves the luminescence characteristics such as the luminance of an organic electroluminescent device, and in particular, it is an aromatic amine derivative represented by the following formula (A) as a dopant compound in a luminescent layer.

(A)

In the above formula (A)

Ar ₁ And Ar ₂ are the same or different from each other and each independently represents a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number An aryl group of 5 to 50 carbon atoms, or a heteroaryl group of 2 to 50 carbon atoms having a substituted or unsubstituted heteroatom, O, N, S, or P, may be used.

Also, according to an embodiment of the present invention, the Ar ₁ And Ar < _{2 >} may combine with each other to form a saturated or unsaturated ring.

X ₁ to X ₈ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 hetero aryl group, Or a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a hydroxyl group, a nitro group, and a halogen group And at least one of X ₁ to X ₈ is a substituent represented by the following formula (Q).

According to an embodiment of the present invention, X ₁ to X ₈ may be bonded to each other or adjacent substituents to form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero.

At least one of X ₁ to X ₄ and at least one of X ₅ to X ₈ in the above formula [A] may be a substituent represented by the following formula [Q], and the substituent Each may be the same or different from each other.

[Structural formula Q]

In the above formula [Q], * denotes a site which binds to X ₁ to X ₈ of the above-mentioned formula [A].

L is a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic arylene group having 2 to 60 carbon atoms, Substituted or unsubstituted C 6 -C 60 arylene group having at least one fused cycloalkyl having 3 to 30 carbon atoms and substituted or unsubstituted C 3 -C 30 cycloalkyl having at least one substituted or unsubstituted C2- And n is an integer of 0 to 2. When n is 2, a plurality of Ls may be the same or different.

R ₁ to R ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 50 carbon atoms An aryl group, or a heteroaryl group having 2 to 50 carbon atoms having a substituted or unsubstituted hetero atom, O, N, S, or P, may be used.

In addition, Ar ₁ and Ar ₂ , X ₁ to X ₈ , R ₁ to R ₂ and L may be connected to adjacent substituents to form a substituted or aromatic monocyclic or polycyclic ring, Group, aromatic group, or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O.

In the above formulas [A] and [Q], the substituted or unsubstituted substituent may be a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a halogenated An alkyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms , Or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, A silyl group, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms.

In the above formula [Q], R ₁ to R ₂ Is a substituted or unsubstituted pyridinyl group or a substituted or unsubstituted 6-membered aromatic heteroaryl group, and two of the 6-membered rings are nitrogen atoms and the remainder are carbon atoms.

According to one embodiment of the present invention, R ₁ to R ₂ Is a substituted or unsubstituted pyridinyl group, the pyridinyl group may be any one selected from the following formulas (2A) to (2C).

[Chemical Formula 2B] < EMI ID =

According to an embodiment of the present invention, R ₁ to R ₂ Is a substituted or unsubstituted 6-membered aromatic heteroaryl group, the heteroaryl group may be any one selected from the following formulas (3A) to (3F).

[Chemical Formula 3B] < EMI ID =

[Chemical Formula 3E] [Chemical Formula 3F]

[Formula A] according to the present invention may be more specifically selected from compounds represented by the following formulas [A-1] to [A-2].

[Formula A-1] [Formula A-2]

L, n, R ₁ and R ₂ and X ₁ to X ₄ in the above formulas (A-1) to (A-2) are the same as defined in the above formula (A).

C ₁ and C ₂ are the same or different from each other and each independently represents a monovalent or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a 5- to 6-membered heteroaromatic ring fused with an aromatic ring, A 6-membered heteroaromatic ring may be selected from the fused monocyclic or polycyclic aromatic rings.

o is an integer of 1 to 3, p is an integer of 1 to 5, q is an integer of 1 to 8, and r is an integer of 1 to 5.

In addition, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, And one or more amine derivatives.

The organic layer containing the aromatic amine derivative compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, . At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the light emitting layer may include a host and a dopant, and the aromatic amine derivative compound of the present invention may be used as a dopant.

In the present invention, the light emitting layer contains a host material together with the compound represented by the formula (A) according to the present invention, and the content of the aromatic amine derivative compound of the present invention in the light emitting layer, that is, the dopant, About 0.01 to about 20 parts by weight, based on the total weight of the composition.

In addition, in the present invention, a known electron transport material can be used as the electron transport layer material, which functions to stably transport electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, [Compound 201], [Compound 202], oxadiazole derivative PBD, BMD, BND and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

Further, the electron transporting layer used in the present invention can be used as the organometallic compound represented by the following formula (C) alone or in combination with the electron transporting layer material.

≪ RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond.

M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom.

OA is a monovalent ligand capable of single bond or coordination bond with M, O is oxygen, A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C30 cycloalkyl, An alkenyl group, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having a hetero atom O, N, or S.

When m is 1 or n = 0 when M is one metal selected from alkali metals and m is 1 or n = 1 when M is a metal selected from alkaline earth metals, or m = 2 and n = 0, and when M is boron or aluminum, m is any one of 1 to 3 and n is any of 0 to 2, and m + n = 3.

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

The Y may be the same or different and independently selected from the following formulas [C1] to [C39].

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

L represents 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 aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms A substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryl group having 3 to 20 carbon atoms, A heteroaryl group, a cyano group, a halogen group, deuterium, and hydrogen, and may be connected to an adjacent substituent by an alkylene or an alkenylene to form a spiro ring or a fused ring.

Hereinafter, an organic electroluminescent device of the present invention will be described with reference to FIG.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG.

First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ] Can be used.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (? -NPD).

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

In addition, the light emitting layer may include a host and a dopant compound represented by Formula (A) according to the present invention, and the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

At this time, the host used in the light emitting layer may be a compound represented by the following formulas (1A) to (1D).

≪ EMI ID =

In the above formula,

Ar _{7 ,} Ar ₈ and Ar ₉ are the same or different and each independently represents a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group or a substituted or unsubstituted C ₂ -C ₆₀ Or a heteroaromatic linking group.

R ₂₁ to R ₃₀ are the same or different from each other and each independently represents a hydrogen atom, a heavy hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, A substituted or unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, a di (substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, a substituted or unsubstituted amino group having 6 to 60 carbon atoms, Or an unsubstituted aryl group having 6 to 60 carbon atoms) amino group, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron And each substituent may form a condensed ring with the adjacent groups.

E, f and g are the same as or different from each other, and each independently 0 or an integer of 1 to 4.

The two sites represented by * in the anthracene may be the same as or different from each other and each independently combine with the P or Q structure to form an anthracene derivative selected from the following formulas (1Aa-1) to (1Aa-3) can do.

[Chemical Formula 1Aa-1] [Chemical Formula 1Aa-2] Chemical Formula 1Aa-3]

The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, An alkyl group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An aryloxy group having 1 to 24 carbon atoms, an arylsilyl group, and an aryloxy group having 1 to 24 carbon atoms.

≪ RTI ID = 0.0 &

In the above formula (1B)

Wherein Ar ₁₇ to Ar ₂₀ are the same or different from each other and each independently represent a substituent group as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ are the same as defined in R ₂₁ to R ₃₀ in Formula 1A Lt; / RTI >

W and ww are the same as or different from each other, x and xx are the same as or different from each other, w + ww and x + xx are the same or different from each other and independently an integer of 0 to 3; Y and yy are the same or different, and z and zz are the same or different from each other, y + yy to z + zz are not more than 2, and each is an integer of 0 to 2;

[Chemical Formula 1C]

In the above formula 1C,

Wherein Ar ₂₁ to Ar ₂₄ are the same or different and are made of the same substituents as defined for Ar ₇ to Ar ₈ in the (1A) each independently from each other, wherein R ₆₄ to R ₆₇ is at R ₂₁ to R ₃₀ of Formula 1A Lt; / RTI > is as defined above.

The above ee to hh are the same as or different from each other, and each independently is an integer of 1 to 4, and the above-mentioned II to 11 are the same or different and independently an integer of 0 to 4.

[Chemical Formula 1D]

In the above formula (1D)

Wherein Ar ₂₅ to Ar ₂₇ are the same or different from each other and each independently represent a substituent group as defined in Ar ₇ to Ar ₈ in formula (1A), and R ₆₈ to R ₇₃ are the same or different from each other, The substituent groups are the same as defined in R ₂₁ to R ₃₀ of 1 A, and each substituent may form a saturated or unsaturated cyclic structure adjacent to each other. In addition, the mm to ss are the same or different from each other and each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group consisting of the following [host 1] to [host 56], but is not limited thereto.

[Host 1] [Host 2] [Host 3] [Host 4]

[Host 5] [Host 6] [Host 7] [Host 8]

[Host 9] [Host 10] [Host 11] [Host 12]

[Host 13] [Host 14] [Host 15] [Host 16]

[Host 17] [Host 18] [Host 19] [Host 20]

[Host 21] [Host 22] [Host 23] [Host 24]

[Host 25] [Host 26] [Host 27] [Host 28]

[Host 29] [Host 30] [Host 31] [Host 32]

[Host 33] [Host 34] [Host 35] [Host 36]

[Host 37] [Host 38] [Host 39] [Host 40]

[Host 41] [Host 42] [Host 43] [Host 44]

[Host 45] [host 46] [host 47] [host 48]

[Host 49] [host 50] [host 51] [host 52]

[Host 53] [Host 54] [Host 55] [Host 56]

At least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process, Means a method of forming a thin film by evaporating a material used as a material for forming each of the layers by heating or the like under a vacuum or a low pressure state and the solution process is used as a material for forming each of the layers Means a method of forming a thin film by a method such as ink jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating and the like.

Further, the organic electroluminescent device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, and a single color or white flexible illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1. Synthesis of Compound 1

Synthesis Example 1-1. Synthesis of intermediate 1-a

Intermediate 1-a

1-naphthaleneboronic acid (31.5 g, 183.2 mmol) and tetrakis (triphenylphosphine) palladium (8.8 g, 7.62 mmol) were added to 1 L of toluene, Lt; / RTI &gt; 2 M Potassium carbonate (228 mL, 458 mmol) and 228 mL of ethanol were added and refluxed for 5 hours. After cooling to room temperature, it was extracted with ethyl acetate. Separation by column chromatography gave Intermediate 1-a (35 g, 87%).

Synthesis Example 1-2. Synthesis of Intermediate 1-b

Intermediate 1-b

3-Bromo-6-methylpyridine (38.5 g, 224 mmol) was added, and 400 mL of tetrahydrofuran was added thereto, followed by cooling to -78 ° C. 130 mL of normal-butyl lithium was slowly added dropwise, followed by stirring at the same temperature for about 30 minutes. Intermediate 1-a (21.0 g, 80 mmol) was added thereto, followed by stirring at room temperature for 1 hour. Extraction with dichloromethane afforded intermediate 1-b (26.6 g 80%).

Synthesis Example 1-3. Synthesis of Intermediate 1-c

Intermediate 1-c

300 mL of acetic acid and 0.2 mL of hydrochloric acid were added dropwise to intermediate 1-b (29.1 g, 70 mmol), and the temperature was raised to 80 ° C. The mixture was stirred for 3 hours and then filtered. Washed with distilled water and methanol, and then recrystallized from acetone to obtain intermediate 1-c (27.9 g, 80%).

Synthesis Example 1-4. Synthesis of intermediate 1-d

Intermediate 1-d

Intermediate 1-c (21.9 g, 0.055 mol) was added to 250 mL of dimethylformamide and stirred at 0 ° C. En-bromosuccinimide (21.5 g, 0.121 mol) was dissolved in 70 mL of dimethylformamide, and the mixture was stirred for 6 hours. The distilled water was filtered and washed with hexane. Dissolved in dichloromethane, heated and treated with acid clay and activated carbon. Washed with dichloromethane and recrystallized with hexane to obtain intermediate 1-d (16.5 g, 54%).

Synthesis Example 1-5. Synthesis of Intermediate 1-e

Intermediate 1-e

(13.8 g, 0.1 mol), 2-methyl-5-aminopyridine (10.8 g, 0.1 mol), palladium acetate (0.08 g, 0.32 mmol), 2,2'-bis (0.26 g, 0.42 mmol) and sodium tertiary butoxide (15.2 g, 0.16 mol) were added to 150 mL of toluene and refluxed for 12 hours. The mixture was cooled to room temperature, washed with methanol, and recrystallized from dichloromethane and methanol to obtain Intermediate 1-e (15.3 g, 73%).

Synthesis Example 1-6. Synthesis of Compound 1

Compound 1

Intermediate 1-d (5.3 g, 9.5 mmol), Intermediate 1-e (5.2 g, 24.8 mmol) and palladium acetate (0.15 g, 0.67 mmol) were added to 80 mL of toluene and stirred at 60 ° C. Tritosphate (0.42 g, 1.9 mmol) and potassium tertiary butoxide (4.2 g, 38.1 mmol) were slowly added dropwise and reacted at 100 ° C. for 2 hours. The mixture was extracted with dichloromethane and then subjected to column chromatography to obtain Compound 1 (4.9 g, 64%).

MS (MALDI-TOF): m / z 812.34 [M] ^&lt; ^{+ &}

Synthesis Example 2. Synthesis of Compound 2

Bromobenzene was used in place of the 3-bromo-6-methylpyridine used in the above Synthesis Example 1-2, and 3-chloro-6-chlorobenzene instead of 1-cyano- -Methylpyridine and 4-aminoquinoline was used instead of 2-methyl-5-aminopyridine, Compound 2 (yield 65%) was obtained in the same manner as in Synthesis Example 1.

MS (MALDI-TOF): m / z 834.35 [M] ^&lt; ^{+ &}

Synthesis Example 3. Synthesis of Compound 3

Except that 1-bromobenzene was used in place of 3-bromo-6-methylpyridine used in Synthesis Example 1-2, and 4-bromopyrimidine instead of 1-cyano- (Yield: 64%) was obtained in the same manner as in Synthesis Example 1, except that 3-cyanophenylamine was used instead of 2-methyl-5-aminopyridine.

MS (MALDI-TOF): m / z 756.27 [M] ^&lt; ^{+ &}

Synthesis Example 4. Synthesis of Compound 4

Synthesis Example 4-1. Synthesis of intermediate 4-a

Intermediate 4-a

Intermediate 4-a (yield 90%) was obtained in the same manner as in Synthesis Example 1-1, except for using methyl-5-bromo-2-iodobenzoate instead of methyl-2-bromobenzoate.

Synthesis Example 4-2. Synthesis of intermediate 4-b

Intermediate 4-b

Intermediate 4-a (8.5 g, 25 mmol) and sodium hydroxide (1.2 g, 30 mmol) were added to 100 mL of ethanol and refluxed for 6 hours. The temperature was lowered to room temperature and acidified with 2 M hydrochloric acid. The precipitate was filtered and recrystallized from ethanol to give intermediate 4-b (7.8 g, 96%).

Synthesis Example 4-3. Synthesis of intermediate 4-c

Intermediate 4-c

Intermediate 4-b (7.8 g, 25 mmol) was dissolved in 250 mL of methanesulfonic acid, stirred for 24 hours, poured into ice water and precipitated. The precipitated solids were filtered and washed with distilled water, and an aqueous solution of sodium hydrogencarbonate was added thereto, followed by stirring for 3 hours. After filtration, it is neutralized with distilled water. Recrystallization from acetic acid gave Intermediate 4-c (5.4 g, 70%).

Synthesis Example 4-4. Synthesis of intermediate 4-d

Intermediate 4-d

Intermediate 4-d (yield: 70%) was obtained in the same manner as Intermediate 4-c synthesized in Synthesis Example 4-3, instead of Intermediate 1-c used in Synthesis Example 1-4.

Synthesis Example 4-5. Synthesis of intermediate 4-e

Intermediate 4-e

Intermediate 4-d (4.7 g, 12.2 mmol) was added to 50 mL of tetrahydrofuran, n-butyllithium (5.8 mL, 14.6 mmol) was added dropwise at -78 째 C, and the mixture was stirred for about 1 hour. A solution of 9-fluorenone (1.9 g, 10.8 mmol) dissolved in 20 mL of tetrahydrofuran was slowly added dropwise at the same temperature, followed by stirring for 2 hours and then stirring at room temperature for 12 hours. Extraction with ethyl acetate followed by recrystallization with diethyl ether gave Intermediate 4-e (5.2 g, 78%).

Synthesis Example 4-6. Synthesis of intermediate 4-f

Intermediate 4-f

Intermediate 4-f (yield 92%) was obtained in the same manner as Intermediate 4-e synthesized in Synthesis Example 4-5, instead of Intermediate 1-b used in Synthesis Example 1-3.

Synthesis Example 4-7. Synthesis of Compound 4

Except that 6-chloro-3-methylpyridazine was used in place of 1-cyano-4-chlorobenzene used in Synthesis Example 1-5 and 1-naphthalenamine was used instead of 2-methyl- Compound 4 (yield: 62%) was obtained in the same manner as in Synthesis Example 1.

MS (MALDI-TOF): m / z 832.33 [M] ^&lt; ^{+ &}

Synthesis Example 5. Synthesis of Compound 5

Synthesis Example 5-1 Synthesis of Intermediate 5-a

Intermediate 5-a

Intermediate 4-c was used instead of Intermediate 4-d used in Synthesis Example 4-5 and 3-methyl-9H-indeno [2,1-c] pyridin-9-one was used instead of 9- To obtain Intermediate 5-a (yield: 76%).

Synthesis Example 5-2 Synthesis of Intermediate 5-b

Intermediate 5-b

Intermediate 5-b (yield 90%) was obtained in the same manner as Intermediate 5-a synthesized in Synthesis Example 5-1 instead of Intermediate 1-b used in Synthesis Example 1-3.

Synthesis Example 5-3 Synthesis of Intermediate 5-c

Intermediate 5-c

Instead of the 1-cyano-4-chlorobenzene used in Synthesis Example 1-5 and using 1-amino-4-methylbenzene instead of 2-methyl-5-amine pyridine, Intermediate 5-c (yield 75%) was obtained.

Synthesis Example 5-4 Synthesis of Intermediate 5-d

Intermediate 5-d

Intermediate 5-b synthesized in Synthesis Example 5-2 was used instead of Intermediate 1-d used in Synthesis Example 1-6, and Intermediate 5-c synthesized in Synthesis Example 5-3 was used instead of Intermediate 1-e And the intermediate 5-d (yield: 77%) was obtained in the same manner.

Synthesis Example 5-5 Synthesis of Intermediate 5-e

Intermediate 5-e

Intermediate 5-e (yield: 60%) was obtained in the same manner as Intermediate 5-d synthesized in Synthesis Example 5-4, in place of Intermediate 1-c used in Synthesis Example 1-4.

Synthesis Example 5-6 Synthesis of Intermediate 5-f

Intermediate 5-f

Except that 2-chloro-4,6-dimethylpyridine was used instead of 1-cyano-4-chlorobenzene used in Synthesis Example 1-5, 4-amino-tertiary butylbenzene was used instead of 2- , The intermediate 5-f (yield: 76%) was obtained in the same manner.

Synthesis Example 5-7 Synthesis of Compound 5

Compound 5

Intermediate 5-e synthesized in Synthesis Example 5-5 was used instead of Intermediate 1-d used in Synthesis Example 1-6, and Intermediate 5-f synthesized in Synthesis 5-6 was used instead of Intermediate 1-e To obtain Compound 5 (yield 69%) in the same manner.

MS (MALDI-TOF): m / z 820.43 [M] ^&lt; ^{+ &}

Synthesis Example 6. Synthesis of Compound 6

Except that 9-fluorenone was used instead of 3-methyl-9H-indeno [2,1-c] pyridin-9-one used in Synthesis Example 5-1, and instead of pentaduteolechlorobenzene used in Synthesis Example 5-3 Methyl-3-pyridineamine was used in place of 1-amino-4-methylbenzene, and in the same manner as Synthesis Example 5-6 except that 6-methyl-3-pyridineamine was used in place of 2-chloro-4,6- (Yield 64%) was obtained in the same manner as in Synthesis Example 5, except that 1-amino-3-methylbenzene was used instead of 4-amino-tert-butylbenzene.

MS (MALDI-TOF): m / z 858.37 [M] ^&lt; ^{+ &}

Synthesis Example 7: Synthesis of Compound 7

Except that 9-fluorenone was used instead of 3-methyl-9H-indeno [2,1-c] pyridin-9-one used in Synthesis Example 5-1, and instead of pentaduteolechlorobenzene used in Synthesis Example 5-3 Bromo-2-methylpyrazine and 2- (3-fluorophenyl) pyridin-4-amine instead of 1-amino-4-methylbenzene and 2- Was obtained in the same manner as in Synthesis Example 5, except that 4-bromo 2-methylpyrimidine was used instead of 4,6-dimethylpyridine and 1-naphthalenamine (D7) was used in place of 4-amino- 7 (yield: 63%).

MS (MALDI-TOF): m / z 886.39 [M] ^&lt; ^{+ &}

Synthesis Example 8. Synthesis of Compound 8

Synthesis Example 4 was repeated except that 3-bromo-6-methylpyridine was used instead of 6-chloro-3-methylpyridazine used in Synthesis Example 4-6 and 2-naphthalenamine was used instead of 1- Compound 8 (yield 64%) was obtained in the same manner.

MS (MALDI-TOF): m / z 832.36 [M] ^&lt; ^{+ &}

Synthesis Example 9 Synthesis of Compound 9

Methyl-9H-indeno [2,1-c] pyridin-9-one was used in place of 9-fluorenone used in Synthesis Example 4-5, Compound 9 (yield: 66%) was obtained in the same manner as in Synthesis Example 4, except that 2-bromo-5-trimethylsilylpyridine was used instead of methylpyridazine and 1-amino-3-methylbenzene was used instead of 1- ).

MS (MALDI-TOF): m / z 889.40 [M] ^&lt; ⁺ & gt ^;

Examples 1 to 9: Preparation of organic light emitting diode

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was pressurized to have a pressure of 1 x 10 &lt; ^-6 &gt; torr, and then DNTPD (700 ANGSTROM), alpha -NPD (300 ANGSTROM), BH1 as a host for the light emitting layer, One of the compounds 1 to 9 (3 wt%) was co-deposited (300 Å), and then Alq ₃ (350 Å), LiF (5 Å) and Al (1,000 Å) were sequentially deposited and measured at 0.4 mA . The DNTPD, the structure of α-NPD, BH1, Alq ₃ and the compounds (1) to compound 9 is as follows.

[DNTPD] [[alpha] -NPD]

[BH1] [Alq _3]

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

Comparative Example 1

The organic luminescent device for Comparative Example 1 was fabricated in the same manner as in Example 1 except that the following compound [101] was used instead of the compound produced by the invention in the device structures of Examples 1 to 9, and the structure thereof is as follows.

[Compound 101]

Voltage, luminance, quantum efficiency, color coordinates, and lifetime of the organic light emitting device manufactured according to Examples 1 to 9 and Comparative Example 1 were measured, and the results are shown in Table 1 below.

division Host Dopant Voltage (V) Brightness (Cd / m2) Quantum efficiency CIE x CIE y Example 1 BH1 Compound 1 3.7 820 7.8 0.14 0.13 Example 2 BH1 Compound 2 3.6 850 7.9 0.14 0.13 Example 3 BH1 Compound 3 3.7 832 7.7 0.14 0.14 Example 4 BH1 Compound 4 3.7 845 7.9 0.14 0.13 Example 5 BH1 Compound 5 3.7 832 8.1 0.14 0.13 Example 6 BH1 Compound 6 3.8 855 8.0 0.14 0.14 Example 7 BH1 Compound 7 3.7 848 8.2 0.14 0.13 Example 8 BH1 Compound 8 3.7 872 8.3 0.14 0.13 Example 9 BH1 Compound 9 3.8 863 7.9 0.14 0.14 Comparative Example 1 BH1 Compound 101 3.7 530 6.0 0.14 0.14

Claims (12)

An aromatic amine derivative represented by the following formula (A)
(A)

In the above formula (A)
Ar ₁ And Ar ₂ are the same or different from each other and each independently represents a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number An aryl group having 5 to 50 carbon atoms, a heteroaryl group having 2 to 50 carbon atoms having a substituted or unsubstituted hetero atom, O, N, S, or P,
X ₁ to X ₈ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30 hetero aryl group, Or a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a hydroxyl group, a nitro group, and a halogen group At least one of X ₁ to X ₈ is a substituent represented by the following formula [Q]
[Structural formula Q]

In the above formula [Q]
* Means a site bound to X ₁ to X ₈ of the above formula (A)
L is a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic arylene group having 2 to 60 carbon atoms, Substituted or unsubstituted C 6 -C 60 arylene group having at least one fused cycloalkyl having 3 to 30 carbon atoms and substituted or unsubstituted C 3 -C 30 cycloalkyl having at least one substituted or unsubstituted C2- And n is an integer of 0 to 2. When n is 2, a plurality of L's are the same or different,
R ₁ to R ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 50 carbon atoms An aryl group, or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having a hetero atom O, N, S, or P,
The above Ar ₁ and Ar ₂ , X ₁ to X ₈ , R ₁ to R ₂ and L may be connected to adjacent substituents to form a substituted or aromatic monocyclic or polycyclic ring, The carbon atom of the aromatic monocyclic or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O,
In the above formulas (A) and (Q)
The substituted or unsubstituted substituent is selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, An aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, To an aryloxy group having 1 to 24 carbon atoms. The method according to claim 1,
The Ar ₁ And Ar ₂ are bonded to each other to form a saturated or unsaturated ring. The method according to claim 1,
Wherein R ₁ to R ₂ and X ₁ to X ₈ are bonded to each other or adjacent substituents to form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero. The method according to claim 1,
At least one of X ₁ to X ₄ and at least one of X ₅ to X ₈ in the above formula [A] is a substituent represented by the above formula [Q], and each of the substituents represented by the above formula [Q] Lt; RTI ID = 0.0 &gt; (I) &lt; / RTI &gt; The method according to claim 1,
The aromatic amine derivative represented by the above formula (A) is any one selected from the following formulas (A-1) to (A-2)
[Formula A-1] [Formula A-2]

In the above formulas A-1 to A-2,
L, n, R ₁ and R ₂ , X ₁ to X ₄ are the same as defined in the above-mentioned formula (A)
C ₁ and C ₂ are the same or different from each other and each independently represents a monovalent or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a 5- to 6-membered heteroaromatic ring fused with an aromatic ring, A 6-membered heteroaromatic ring may be selected from a fused monocyclic or polycyclic aromatic ring,
o is an integer of 1 to 3, p is an integer of 1 to 5, q is an integer of 1 to 8, and r is an integer of 1 to 5. The method according to claim 1,
In the above formula [Q], R ₁ to R ₂ At least one of them is a substituted or unsubstituted pyridinyl group or a substituted or unsubstituted six-membered aromatic heteroaryl group, and two of the six-membered rings are a nitrogen atom and the remainder are carbon atoms. The method according to claim 6,
R ₁ to R ₂ Is a substituted or unsubstituted pyridinyl group, the pyridinyl group is any one selected from the group consisting of the following formulas (2A) to (2C):

[Chemical Formula 2B] &lt; EMI ID = The method according to claim 6,
R ₁ to R ₂ Is a substituted or unsubstituted 6-membered aromatic heteroaryl group, the heteroaryl group is any one selected from the following formulas (3A) to (3F):

[Chemical Formula 3B] &lt; EMI ID =

[Chemical Formula 3E] [Chemical Formula 3F] A first electrode; A second electrode facing the first electrode; And an organic layer interposed between the first electrode and the second electrode,
The organic electroluminescent device according to claim 1, wherein the organic layer comprises at least one aromatic amine derivative compound. 10. The method of claim 9,
Wherein the organic layer comprises at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, and an electron injecting layer. 10. The method of claim 9,
Wherein the organic layer interposed between the first electrode and the second electrode includes a light emitting layer, the light emitting layer comprises a host and a dopant, and the aromatic amine derivative compound is used as a dopant. 10. The method of claim 9,
Wherein the organic electroluminescent device is used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, and a monochromatic or white flexible illumination device.

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