KR20140076170A - Pyrene compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a pyrene-based arylamine compound represented by formula 1 and an organic electroluminescent device using the same containing an electron-attracting group and deuterium or a deuterium-substituted aryl group, thereby maximizing blue purity and improving lifetime property. The organic electroluminescent device according to the present invention has excellent blue color purity and long lifetime property, thereby being effectively used for various displays and lights.

Description

[0001] The present invention relates to a pyrene-based compound and an organic electroluminescent device using the same,

The present invention relates to a pyrene-based compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a pyrene-based blue light emitting compound having excellent blue purity and improved lifetime characteristics, and an organic electroluminescent device using the same.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of display devices. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT. However, And it is necessary to be sure.

On the other hand, the organic electroluminescent device, which is a new flat display device, is a display using a self-luminescent phenomenon, has a wide viewing angle, is thinner than a liquid crystal display, can be made small and has a fast response speed. Application to color display or illumination is expected. For this purpose, there is a growing need for high luminance, high efficiency and high color purity blue light emitting materials.

US Patent No. 7053255 discloses a blue light emitting compound having a diphenyl anthracene structure in which an aryl group is substituted at the terminal thereof and an organic electroluminescent device using the blue light emitting material. However, there is a problem in that the luminous efficiency and brightness are not sufficient , And US Pat. Nos. US 7233019 and 2006-0006760 disclose an organic electroluminescent device using a substituted pyrene-based compound. However, since the color purity of blue is low and it is difficult to realize a deep blue color, There is a problem in implementing the display.

A problem to be solved by the present invention is to provide a novel pyrene-based blue light emitting compound which can maximize color purity and at the same time have a long life span by overcoming the problem that the lifetime characteristic becomes shorter as the blue purity becomes better in the conventional blue light emitting material .

Another object of the present invention is to provide an organic electroluminescent device using the novel pyrene blue light emitting compound.

In order to solve the above problems,

There is provided a pyrene-based arylamine compound represented by the following Chemical Formula 1 and containing an electron-withdrawing group and an aryl group substituted with deuterium or deuterium at the same time.

[Chemical Formula 1]

Also, the present invention provides an organic thin film layer for an organic electroluminescence device, which comprises at least one of the above-mentioned pyrene-based arylamine compounds and, when the pyrene-based arylamine compound is used as a dopant, There is provided an organic film layer comprising at least one host compound represented by any one of the following Chemical Formulas 1A to 1D.

≪ EMI ID =

≪ RTI ID = 0.0 &

[Chemical Formula 1C]

[Chemical Formula 1D]

Each substituent in the above formulas (1) and (1A) to (1D) will be described later.

The organic electroluminescent device comprising the pyrene-based compound of the formula (1) according to the present invention has excellent color purity of blue and excellent lifetime characteristics and can be used for various displays and illumination.

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

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

The pyrene-based arylamine light-emitting compound according to the present invention is represented by the above-mentioned formula (1), and includes an electron-withdrawing group and an aryl group substituted with deuterium or deuterium at the same time, thereby maximizing blue purity and improving lifetime characteristics.

The pyrene-based arylamine light-emitting compound according to the present invention includes electron-withdrawing groups on the substituted aryl groups on both sides of the amino group, thereby broadening the bandgap between HOMO and LUMO, thereby maximizing the blue purity of the light-emitting compound. In general, when the color purity is improved, the lifetime of the luminescent compound is shortened. However, the pyrene-based arylamine compound according to the present invention maximizes blue purity by introducing an electron-withdrawing group, An aryl group substituted with deuterium or deuterium is introduced into the carbon-hydrogen bond to increase the intramolecular bonding force, thereby improving lifetime characteristics.

Further, the organic electroluminescent device according to the present invention includes an anode; Cathode; And a layer containing a pyrene-based arylamine compound represented by the above-mentioned formula (1) between an anode and a cathode. Since the blue light-emitting compound has excellent color purity and long life characteristics, There are advantages that can be applied.

Specifically, the pyrene-based arylamine compound according to the present invention is characterized by being a compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

로 치환되며, 상기 Ar2는 R로 치환되는 것을 특징으로 한다.The Ar1 And Ar2 are each independently selected from the group consisting of phenyl, naphthyl, phenanthryl, fluoranthenyl and fluorenyl, Ar1 is selected from the group consisting of R and

, And Ar2 is substituted with R.

The R is a substituent selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an electron withdrawing group (EWG) ,

The electron-withdrawing group (EWG) of the substituent R serves to weaken the electron density, and may be a halogen group, -CF ₃ or cyano group, thereby maximizing the color purity of the luminescent compound, Hydrogen bond between the carbon-hydrogen bonds is increased by the deuterium or deuterium-substituted aryl groups, and the lifetime characteristics are simultaneously improved.

Therefore, And Ar2 is characterized in that it comprises at least one electron-withdrawing group selected from halogen, -CF ₃ and cyano group independently.

The above-mentioned m and n are integers of 1 or 2.

Further, the Ar1 And Ar2 each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, And a silyl group, and the further substituted substituent may be bonded to adjacent adjacent substituents Ar1 _, Ar2 and R to form a saturated or unsaturated ring.

The pyrene-based arylamine compound represented by the formula (1) according to the present invention is not limited to the range of the present invention, but the pyrene-based arylamine compound represented by the above formulas (2) to Or the like.

[Chemical Formula 2] < EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A stearyl group, a trichloromethyl group, and a trifluoromethyl group.

Specific examples of the cycloalkyl group as the substituent used in the compound of the present invention include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and an adamantyl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, .

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, or a benzoimidazole group, have.

The organic electroluminescent device according to the present invention includes an anode; Cathode; And a pyrene-based arylamine compound according to the above formula (1) between the anode and the cathode.

At this time, the pyrene-based arylamine compound according to an embodiment of the present invention is preferably included in the light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, a hole blocking layer, A hole transporting layer, an electron transporting layer, an electron injecting layer, and an electron blocking layer.

According to another embodiment of the present invention, the light emitting layer may further include at least one compound selected from compounds represented by the following formulas (IA) to (1D).

≪ EMI ID =

≪ RTI ID = 0.0 &

[Chemical Formula 1C]

[Chemical Formula 1D]

X 1 to X 10 are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group having 1-30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5-30 carbon atoms, a substituted or unsubstituted alkylamine group having 1-30 carbon atoms, An arylamine group having 5-30 carbon atoms, a substituted or unsubstituted aryl group having 5-50 carbon atoms, a heteroaryl group having 3-50 carbon atoms having a substituted or unsubstituted heteroatom, O, N or S, Substituted silicon group, substituted or unsubstituted boron , It is selected from substituted or unsubstituted silane group, a carbonyl group, a phosphonium group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, an amide group and an ester group.

In addition, X1 to X10 may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

In the above formula (1B), Ar17 to Ar20 are the same or different and each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R60 to R63 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 carboxyl group or a salt thereof, A substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, An unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23), and -N (R24) (R25).

R 21 to R 25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted group having 2-60 carbon atoms A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, an alkynyl group, a substituted or unsubstituted alkoxy group having 1-60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-60 carbon atoms, a substituted or unsubstituted aryl group having 5-60 carbon atoms, A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

W and ww are the same or different from each other, and x and xx are the same 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;

In the above formula (1C), Ar 21 to Ar 24 are the same or different and are independently selected from the group consisting of a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R64 to R67 are the same or different 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 carboxyl group or a salt thereof, A substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, An unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23), and -N (R24) (R25).

R 21 to R 25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted group having 2-60 carbon atoms A substituted or unsubstituted alkoxy 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 5 to 60 carbon atoms, a substituted or unsubstituted 5- to 5- A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

Ee to hh are the same as or different from each other, and each independently is an integer of 1 to 4, and ii to 11 are the same or different and independently an integer of 0 to 4;

In the above formula (1D), Ar 25 to Ar 27 are the same or different and each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R 68 to R 73 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 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, An unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23), and -N (R24) (R25).

R 21 to R 25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted group having 2-60 carbon atoms A substituted or unsubstituted alkoxy 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 5 to 60 carbon atoms, a substituted or unsubstituted 5- to 5- A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

Each of R21 to R25 may be connected to adjacent substituents to form a saturated or unsaturated cyclic structure.

Also, mm to ss are the same as or different from each other, and each independently an integer of 0 to 4.

According to a preferred embodiment, the formula (1A) may be selected from compounds represented by the following formulas (1Aa) to (1Ae).

≪ RTI ID = 0.0 &

≪ RTI ID = 0.0 &

[Chemical Formula 1 Ac]

[Formula 1Ad]

≪ RTI ID = 0.0 &

In the formula [1Aa], Ar7 and Ar8 are the same or different and are each independently selected from substituted or unsubstituted aromatic linking groups having 5-60 carbon atoms and substituted or unsubstituted heteroaromatic linking groups having 2-60 carbon atoms.

R 21 to R 30 are the same as or different from each other and each independently represent the same definitions as defined for X 1 to X 10, and e and f are the same or different and independently an integer of 0 to 4;

Wherein Ar9 and Ar10 are the same as or different from each other, and each independently is the same as defined in the above Ar7 to Ar8, and R31 to R40 are the same as or different from each other, and each independently is the same as defined in X1 to X10 G and h are the same or different and each independently an integer of 0 to 4, and each of the substituents may be connected to adjacent substituents to form a saturated or unsaturated cyclic structure, Each independently substituted substituent is bonded to the 9-position and the 10-position of the anthracene, so that the symmetrical group is not bonded to the anthracene phase.

In the above formula (1), Ar11 to Ar12 are the same as or different from each other, and each independently is the same as defined in the above Ar7 to Ar8, i and j are the same as or different from each other, and each independently is an integer of 1 to 4.

In addition, one of the substituents of c1 to c4 binds to the * moiety of the formula Ac and X is selected from -O-, -S-, -N (R50) - and -N (R51R52) And k is an integer of 1 to 4. When k is 2 or more, the two or more R42 to R49 are the same as or different from each other.

Wherein Ar13 and Ar14 are the same as or different from each other and each independently is the same as defined in Ar7 to Ar8, R53 and R54 are the same as defined in X1 to X10, L and m are the same as or different from each other, And P and q are the same or different from each other and each independently an integer of 0 to 4;

Is a single bond, -O-, -S-, -N (R55) -, an alkylene group or an arylene group, and r is 2 or 3, and in this case, They may be the same or different, and * the sites are connected to each other.

And R < 59 > are the same or different from each other and each independently is the same as defined in X1 to X10, and u is an integer of 1 to 3, And s and t are independently an integer of 0 to 4, and when s, t, u, and v are each independently 2 or more, A15 And A16 and R56 to R59 may be the same or different.

According to a more preferred embodiment, the compounds represented by the formulas (IA) to (1D) may be any one selected from the following compounds [1] to [310].

According to a preferred embodiment, the organic electroluminescent device according to the present invention includes the organic thin film layer between the anode and the cathode as a light emitting layer, and a hole injecting layer, a hole transporting layer, a hole blocking layer, , An electron injection layer, and an electron blocking layer.

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the material of the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, CuPc or starburst type amines such as TCTA and m-MTDATA may be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, . The material for the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

On the other hand, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to one embodiment of the present invention can be used for a display device, a display device, a monochrome or white illumination device, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic light emitting diode according to the present invention includes an anode 20, a hole transporting layer 40, an organic light emitting layer 50, an electron transporting layer 60 and a cathode 80, An injection 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.

Referring to FIG. 1, the organic electroluminescent device of the present invention and its manufacturing method will be described as follows.

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), and zinc oxide (ZnO), 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.

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.

When the holes pass through the organic light emitting layer and enter the cathode, the lifetime and efficiency of the hole blocking layer are reduced. Therefore, the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO level. The hole blocking material used herein is not particularly limited, but it is required to have an ionization potential higher than that of a light emitting compound while having an 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.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.

Synthesis Example 1. Synthesis of [Formula 3]

Synthesis Example 1 (1) 2,4-di (phenyl -d ₅₎ Synthesis of 6-fluoro aniline

1L round bottom flask was charged with 2,4-dibromo-6-fluoro-aniline in 30 g (111.56 mmol), phenylboronic acid _{-d 5 31.2 g (245.44 mmol)} , potassium carbonate _{(K 2 CO 3) 61.9 g} (446.27 mmol ), 2.6 g (2.20 mmol) of tetrakistriphenylphosphine palladium (Pd (PPh3) 4), 120 mL of water, 300 mL of toluene and 300 mL of tetrahydrofuran were added and refluxed for 24 hours. After completion of the reaction, the reaction product was separated to remove the water layer, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. The result was dried to obtain 24.2 g 79.4% of a white solid was obtained.

Synthesis Example 1- (2) Synthesis of N- [2,4-di (phenyl-d ₅ ) -6-fluorophenyl] -N- (4-fluorophenyl)

20.0 g (73.16 mmol) of 2,4-di (phenyl-d ₅ ) -6-fluoroaniline prepared in Example 1- (1) above, 13.2 g of 4-fluorobromobenzene 76.82 mmol), palladium acetate {Pd (OAc) ₂ } 0.33 g (1.46 mmol), sodium tertiary butoxide 14.06 g (146.32 mmol), 2,2'-bisdiphenylphosphino-1,1'- 0.91 g (1.46 mmol) of t-butyl and 180 mL of toluene were put in and refluxed for 24 hours. After the reaction was completed, the reaction mixture was filtered under a hot condition. The toluene was concentrated under reduced pressure and then separated by column chromatography. The residue was dissolved in dichloromethane and hexane was added thereto to precipitate crystals. After filtration and drying, 19.0 g of white A solid was obtained.

Synthesis of Synthesis Example 1- (3) [Formula 3]

500 mL of N- prepared in Example 1- (2) To a round bottom flask was added [2,4-di (phenyl -d ₅₎ -6-fluoro-phenyl] -N- (4-fluorophenyl) amine A solution of 5.23 g (26.67 mmol) of 1-bromopyrene, 22.22 mmol of 1-bromopyrene, 0.05 g (0.22 mmol) of palladium acetate {Pd (OAc) ₂ , 4.27 g (44.45 mmol) of sodium tertiary butoxide, 0.09 g (0.45 mmol) of silylbutylphosphine and 200 mL of toluene were charged and refluxed for 24 hours. When the reaction was completed, the temperature was lowered to room temperature and crystals were formed when crystals were formed. The filtered crystals were dissolved in toluene, and ethanol was added to precipitate crystals. The crystals were collected by filtration and dried to obtain 5.7 g (yield 50.3%) of pale yellow solid.

MS (MALDI-TOF): m / z 567.3 [M] ^< ^{+ &}

Synthesis Example 2. Synthesis of [Formula 4]

(4) was synthesized in the same manner as in the synthesis of the compound of the formula (3), except that 4-cyanobromobenzene-d4 was used instead of 4-fluorobromobenzene in the synthesis example 1- (2).

MS (MALDI-TOF): m / z 578.3 [M] ^< ^{+ &}

Synthesis Example 3. Synthesis of [Formula 8]

Fluorobromobenzene was used instead of 2,4-dibromo-6-fluoroaniline in Synthesis Examples 1- (1) and 1- (2), 2,4-dibromo-5-fluoro (8) was synthesized in the same manner as in the synthesis of the compound of the formula (3) except that 2-bromo-7-cyano-9,9-dimethylfluorene was used instead of aniline.

MS (MALDI-TOF): m / z 690.3 [M] ^< ⁺ & gt ^;

Synthesis Example 4. Synthesis of [Formula 10]

Bromo-5-trifluoromethylaniline instead of 2,4-dibromo-6-fluoroaniline and 1-bromoprene in Synthesis Examples 1- (1) and 1- (3) (10) was synthesized in the same manner as in the synthesis of the compound of formula (3), except that dibromopyran was used.

MS (MALDI-TOF): m / z 870.3 [M] ^< ⁺ & gt ^;

Synthesis Example 5. Synthesis of [Formula 12]

Except that 4-cyanobromobenzene-d4 and 1,6-dibromopyrene were used instead of 4-fluorobromobenzene and 1-bromoprene in Synthesis Examples 1- (2) and 1- (3) (12) was synthesized in the same manner as in the synthesis of the compound of formula (3).

MS (MALDI-TOF): m / z 954.5 [M] ^< ^{+ &}

Synthesis Example 6. Synthesis of [Formula 13]

Was obtained in the same manner as in Synthesis Examples 1- (1), 1- (2) and 1- (3) except that 2,4-dibromo-6-fluoroaniline, 4-fluorobromobenzene and 1- (13) was synthesized in the same manner as in the synthesis of the compound of the formula (3), except that 5-fluoroaniline, 4-fluoro-bromonaphthalene and 1,6-dibromopyrene were used.

MS (MALDI-TOF): m / z 870.3 [M] ^< ⁺ & gt ^;

Synthesis Example 7. Synthesis of [Formula 22]

Was obtained in the same manner as in Synthesis Examples 1- (1), 1- (2) and 1- (3) except that 2,4-dibromo-6-fluoroaniline, 4-fluorobromobenzene and 1- (22) was synthesized in the same manner as in the synthesis of the compound of the formula (3), except that 5-fluoroaniline, 4-fluoro-2-methylbromobenzene and 1,6-dibromopyrene were used.

MS (MALDI-TOF): m / z 798.3 [M] ^< ^{+ &}

Synthesis Example 8. Synthesis of [Formula 26]

Was obtained in the same manner as in Synthesis Examples 1- (1), 1- (2) and 1- (3) except that 2,4-dibromo-6-fluoroaniline, 4-fluorobromobenzene and 1- (26) was synthesized in the same manner as in the synthesis of the compound of formula (3) except that 5-fluoroaniline, 3,5-dicyanobromobenzene and 1,6-dibromopyrene were used.

MS (MALDI-TOF): m / z 834.3 [M] ^< ^{+ &}

Synthesis Example 9. Synthesis of [Formula 29]

(3-pyridyl) bromobenzene instead of 4-fluorobromobenzene and 1-bromoprene in Synthesis Examples 1- (2) and 1- (3) (29) was synthesized in the same manner as in the synthesis of the compound (3), except that bromoprene was used.

MS (MALDI-TOF): m / z 1100.5 [M] ^< ⁺ & gt ^;

Example 1: Fabrication of organic electroluminescent device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber, the base pressure was adjusted to 1 × 10 ^-7 torr, and CuPc (800 Å) and α-NPD (300 Å) 3%) were mixed to form a film (250 ANGSTROM) Next, Alq ₃ (350 Å), LiF (5 Å), and Al (500 Å) were sequentially deposited to form an organic electroluminescent device. The luminescent characteristics of the organic electroluminescent device were measured at 0.4 mA.

Examples 2 to 9

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compound shown in [Table 1] was used in place of the compound represented by Formula 3, and the luminescent characteristics were measured under the same conditions as in Example 1.

Comparative Examples 1 to 3

The organic electroluminescent devices were fabricated in the same manner as in Example 1 to 9 using the following [BD1] to [BD3] instead of the pyrene-based arylamine compounds according to the present invention, Lt; / RTI >

[BD1] [BD2] [BD3]

The voltage, current, luminance, color coordinates and lifetime of the organic electroluminescent device manufactured according to Examples 1 to 9 and Comparative Examples 1 to 3 were measured and the results are shown in Table 1 below. T95 means the time required for the luminance to be reduced to 95% of the initial luminance.

division compound V J (mA / cm 2) Cd / ㎡ CIEx CIEy T95 Example 1 (3) 3.71 10 662 0.143 0.110 630 Example 2 Formula 4 3.73 10 607 0.137 0.107 760 Example 3 8 3.72 10 690 0.143 0.115 680 Example 4 10 3.75 10 679 0.142 0.117 705 Example 5 Formula 12 3.72 10 688 0.143 0.115 695 Example 6 Formula 13 3.78 10 738 0.142 0.111 660 Example 7 Formula 22 3.78 10 736 0.142 0.110 730 Example 8 26 3.72 10 638 0.143 0.103 620 Example 9 Formula 29 3.80 10 542 0.139 0.096 608 Comparative Example 1 BD1 3.81 10 796 0.130 0.151 460 Comparative Example 2 BD2 3.82 10 894 0.137 0.146 520 Comparative Example 3 BD3 3.78 10 662 0.133 0.123 420

As can be seen from the results of the above Table 1, the organic electroluminescent device using the pyrene-based arylamine compound according to the present invention exhibits excellent color purity and long life characteristics compared with the conventional blue light emitting compound , Various displays and lights, and the like.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (11)

A pyrene-based arylamine compound represented by the following formula (1) and containing an electron-withdrawing group and an aryl group substituted with deuterium or deuterium simultaneously:
[Chemical Formula 1]

In the above formula (1)
The Ar1 And Ar2 are each independently selected from the group consisting of phenyl, naphthyl, phenanthryl, fluoranthenyl and fluorenyl,
Wherein R is selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an electron withdrawing group (EWG)
Wherein the electron attractive group (EWG) is a halogen group, -CF ₃ and cyano group,
The Ar1 Ar2 is and comprises at least one electron-withdrawing group selected from halogen, -CF ₃ and cyano, each independently,
And m and n are integers of 1 or 2. The method according to claim 1,
The Ar1 And Ar2 each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, And a silyl group, and R < 2 >
Wherein the substituent is bonded to another adjacent substituent, Ar1 _, Ar2 or R to form a saturated or unsaturated ring. The method according to claim 1,
The pyrene-based arylamine compound according to claim 1, wherein the compound represented by formula (1) is any one selected from pyrene compounds represented by the following formulas (2) to (33)
[Chemical Formula 2] < EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

An organic thin film layer for an organic electroluminescence device comprising at least one pyrene based arylamine compound according to any one of claims 1 to 3. 5. The method of claim 4,
Wherein the organic thin film layer contains at least one compound represented by any one of the following Chemical Formulas 1A to 1D:
≪ EMI ID =

≪ RTI ID = 0.0 &

[Chemical Formula 1C]

[Chemical Formula 1D]

In the above formula,
X1 to X10 are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1-30 carbon atoms, a substituted or unsubstituted alkenyl group having 2-30 carbon atoms, a substituted or unsubstituted C3- A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, An amino group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-50 carbon atoms having O, N or S, a substituted or unsubstituted silicon group, A substituted boron group, a substituted or unsubstituted group Selected from a silane group, a carbonyl group, a phosphonium group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, an amide group and an ester group and,
X1 to X10 may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with a group adjacent to each other;

In the above formula (1B)
Ar17 to Ar20 are the same or different and are each independently selected from substituted or unsubstituted aromatic linking groups having 5 to 60 carbon atoms and substituted or unsubstituted heteroaromatic linking groups having 2 to 60 carbon atoms,
R60 to R63 are the same or different from each other and each independently represents a group selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, An arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23) and -N (R24)
R21 to R25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms , A substituted or unsubstituted alkoxy group having 1-60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-60 carbon atoms, a substituted or unsubstituted aryl group having 5-60 carbon atoms, a substituted or unsubstituted 5-60 aryl A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
w and ww are the same 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 each independently an integer of 0 to 3,
y and yy are the same or different from each other, z and zz are the same or different from each other, the value of y + yy to z + zz is 2 or less and each is an integer of 0 to 2;

In the above formula 1C,
Ar21 to Ar24 are the same or different and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms,
R64 to R67 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, An arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23), and -N (R24)
R21 to R25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms , A substituted or unsubstituted alkoxy group having 1-60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-60 carbon atoms, a substituted or unsubstituted aryl group having 5-60 carbon atoms, a substituted or unsubstituted 5- to 60- A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
ee to hh are the same or different from each other and each independently an integer of 1 to 4, ii to 11 are the same or different from each other and each independently an integer of 0 to 4;

In the above formula (1D)
Ar 25 to Ar 27 are the same or different and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms,
R 68 to R 73 are the same or different from each other and each independently represents a group selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, An arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2-60 carbon atoms, -Si (R21) (R22) (R23) and -N (R24)
R21 to R25 are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1-60 carbon atoms, a substituted or unsubstituted alkenyl group having 2-60 carbon atoms, a substituted or unsubstituted alkynyl group having 2-60 carbon atoms , A substituted or unsubstituted alkoxy group having 1-60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-60 carbon atoms, a substituted or unsubstituted aryl group having 5-60 carbon atoms, a substituted or unsubstituted 5- to 60- A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
Each of R21 to R25 may form a saturated or unsaturated cyclic structure by connecting to adjacent substituents,
mm to ss are the same as or different from each other and each independently an integer of 0 to 4; 6. The method of claim 5,
The organic thin film layer for an organic electroluminescence device according to claim 1, wherein the compound represented by the formula (1A) is selected from compounds represented by the following formulas (1Aa) to (1Ae)
≪ RTI ID = 0.0 &

≪ RTI ID = 0.0 &

[Chemical Formula 1 Ac]

[Formula 1Ad]

≪ RTI ID = 0.0 &

In the above formula,
Ar7 and Ar8 are the same or different and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms,
R21 to R30 are the same as or different from each other, and each independently is the same as defined in X1 to X10,
e and f are the same or different from each other and each independently an integer of 0 to 4;

In the above formula,
Ar9 and Ar10 are the same as or different from each other and are each independently the same as defined in Ar7 to Ar8,
R31 to R40 are the same as or different from each other, and each independently is the same as defined in X1 to X10,
g and h are the same or different and independently of each other an integer of 0 to 4,
Each of the substituents may be connected to adjacent substituents to form a saturated or unsaturated cyclic structure. However, in the formula (1Aa), independent substituents are bonded to the 9th and 10th positions of the central anthracene, There is no case where a group which is symmetrical with respect to the surface of the substrate is bonded;

In the above formula (1Ac)
Ar11 to Ar12 are the same as or different from each other, and each independently is the same as defined in the above Ar7 to Ar8; i and j are the same or different from each other and independently an integer of 1 to 4;
one of the substituents of c1 to c4 is bonded to the * moiety of the formula Ac,
X is selected from -O-, -S-, -N (R50) -, and -N (R51R52)
R41 to R49 are the same as or different from each other and are each independently the same as defined in X1 to X10,
k is an integer of 1 to 4, and when k is 2 or more, the two or more R42 to R49 are the same or different from each other;

In the above Formula 1Ad,
Ar13 and Ar14 are the same as or different from each other, and each independently is the same as defined in the above Ar7 to Ar8, R53 and R54 are the same as defined in X1 to X10,
L and m are the same or different from each other and each independently an integer of 1 to 4,
P and q are the same or different from each other and each independently an integer of 0 to 4;

In the above formula,
L2 is a single bond, -O-, -S-, -N (R55) -, an alkylene group or an arylene group and r is 2 or 3, in which case each of the above may be the same or different, * The sites are connected to each other,
Ar15 and Ar16 are the same as or different from each other, and each independently is the same as defined in the above Ar7 to Ar8, and R56 to R59 are the same as or different from each other, and each independently is the same as defined in X1 to X10,
u is an integer of 1 to 4, v is an integer of 1 to 3, s and t are the same as or different from each other and each independently an integer of 0 to 4, and s, t, u and v are each independently 2 In this case, A15 and A16 and R56 to R59 may be the same or different. 6. The method of claim 5,
Wherein the organic thin film layer for organic electroluminescence device is selected from the following [compounds 1] to [310]:

Anode; Cathode; And an organic thin film layer according to claim 4 interposed between the anode and the cathode. 9. The method of claim 8,
The organic electroluminescent device further includes at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer and an electron blocking layer between the anode and the cathode,
Wherein one of the light emitting layer, the hole injecting layer, the hole transporting layer, the hole blocking layer, the electron transporting layer, the electron injecting layer and the electron blocking layer is the organic thin film layer according to claim 8. 10. The method of claim 9,
Wherein the light emitting layer is the organic thin film layer according to claim 4. 9. The method of claim 8,
Wherein the organic electroluminescent device comprises one or more organic electroluminescent layers emitting blue, red or green light to emit white light.

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