KR20070115588A - Blue light emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

A blue light emitting compound is provided to ensure excellent blue color purity and brightness equal to or higher than the conventional light emitting compounds. A blue light emitting compound has a structure represented by the following formula 1. In the formula, each of Ar1 and Ar2 is the formula (a) and the formula (b), and each of A1 and A2 is a C6-14 aryl group or N, S, or O-containing C4-19 heteroaryl group unsubstituted or substituted with a C1-10 alkyl group, C1-10 alkoxy group, or C1-10 heteroalkyl group, wherein each of the substituents is a C1-10 alkyl group, C1-10 alkoxy group, C1-10 alkylamino group, C1-10 alkylsilyl group, C6-14 aryl group, C4-19 heteroaryl group containing N, S, or O, cyano group, or halogen.

Description

Blue light emitting compound and organic electroluminescent device using the same

1 is a schematic diagram of an organic light emitting display device according to an embodiment of the present invention.

<Description of the symbols for the main parts of the drawings>

10: substrate 20: anode

30: hole injection layer 40: hole transport layer

50: organic light emitting layer 60: electron transport layer

70: electron injection layer 80: cathode

The present invention relates to an organic light emitting device, and more particularly, to a blue light emitting compound having excellent blue color purity and an organic light emitting device manufactured using the same.

Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has the advantage of being lighter than a conventional CRT, but has a limited viewing angle. And back light is necessary. In contrast, the organic light emitting diode (OLED), which is a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. Have

Representative organic electroluminescent devices have been restricted to use in various applications since their performance limitations since they were announced by Gurnee in 1969 (US3,172,862, US3,173,050), but in 1987, Eastman Kodak ( Eastman Kodak Co.) 'S multi-layered organic light emitting diode presentation (CW Tang et al., Appl. Phys. Lett., 51, 913 (1987); J. Applied Phys., 65, 3610 (1989)). Overcoming the existing problems has been a rapid development. Currently, organic light emitting diodes have excellent characteristics such as low driving voltage (for example, 10V or less), wide viewing angle, high speed response, and high contrast compared to plasma display panel (PDP) or inorganic electroluminescent display. It can be used as a pixel for graphic displays, as a pixel for television image displays or surface light sources, to form devices on flexible transparent substrates, to be very thin and light, and to produce color Because of this, it is emerging as a suitable device for the next generation flat panel display (FPD).

Such an organic light emitting display device has electrons and holes when electrons and holes are injected into an organic light emitting layer formed between a first electrode (anode), which is a hole injection electrode (anode), and a second electrode (cathode), which is an electron injection electrode (cathode), respectively. Excitons formed in pairs in combination fall and disappear from the excited state to the ground state and emit light. Recently, application to a full-color display is expected. In order to realize full-color, it is necessary to arrange pixels on the panel which emit light of three primary colors of green, red, and blue. A) a method of arranging three types of organic light emitting devices that emit blue, green, and red light; ii) a method of separating light emission from devices exhibiting white light, which is a mixed color of RGB, into three primary colors through a color filter; and iii) blue A method of converting light emission from an organic light emitting device that emits light into green light and red light using a light emitting source has been proposed. In any case, blue light emission is essential and is required for a blue light emitting material having high brightness, high efficiency, and high color purity. The need for it is urgent.

US Patent No. 6,455,720 discloses 2,2- (diaryl) vinylphosphine (2,2- (Diarlyl) vinylphosphine) as a blue light emitting material, and Korean Patent Publication No. KR 2002-0070333 In the center has a diphenyl anthracene structure, a blue light emitting compound having an aryl group substituted in the terminal and an organic light emitting device using the same are disclosed, but there is a problem that the luminous efficiency and luminance is not sufficient.

On the other hand, US Patent Publication No. US 6852429, Republic of Korea Patent Publication No. 2005-0107809 and 2006-0006760 discloses an organic electroluminescent device using a substituted pyrene-based compound, but the blue color purity is low blue Since deep blue is difficult to implement, there is a problem in implementing a full-color display of natural colors.

Therefore, the technical problem to be achieved by the present invention is to provide a blue light emitting compound excellent in color purity of blue.

The second technical problem to be achieved by the present invention is to provide an organic light emitting device using the blue light emitting compound.

The present invention to achieve the first technical problem,

It provides a blue light emitting compound of Formula 1.

또는

이고 Wherein Ar ₁ and Ar ₂ are each

or

ego

A ₁ and A ₂ each represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted carbon atom 4 Heteroaryl group containing -19 N, S, O, The said substituent is a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkylamino group, a C1-C10 alkylsilyl, respectively Group, a C6-C14 aryl group, a C4-C19 N, S, O heteroaryl group, cyano group, or halogen.)

According to an embodiment of the present invention, the blue light emitting compound may be any one selected from the group represented by the following Chemical Formula 2.

,

,

             BD1

,

,

            BD2

,

,

,

,

            BD3 BD4

,

,

,

,

             BD5 BD6

,

,

,

,

             BD7 BD8

,

,

,

,

             BD9 BD10

,

,

,

,

            BD11 BD12

,

,

,

,

            BD13 BD14

,

,

,

,

            BD15 BD16

,

,

            BD17 BD18

,

,

            BD19 BD20

,

,

            BD21 BD22

,

,

            BD23 BD24

,

,

            BD25 BD26

,

,

            BD27 BD28

,

,

            BD29 BD30

,

,

            BD31 BD32

,

,

            BD33 BD34

,

,

            BD35 BD36

,

,

            BD37 BD38

,

,

            BD39 BD40

,

,

           BD41 BD42

According to a preferred embodiment of the present invention, the blue light emitting compound may be any one selected from the group represented by the following formula (3).

,

,

           BD1

     BD2

,

,

           BD7 BD9

,

,

           BD17 BD39

The present invention to achieve the second technical problem,

An organic light emitting display device comprising an anode, an organic light emitting layer, and a cathode, wherein the organic light emitting layer provides an organic light emitting display device including a blue light emitting compound represented by Chemical Formula 1.

The organic light emitting display device according to the present invention may further include a host compound represented by the following Chemical Formula 4 in the organic light emitting layer.

  BH-1

or

                 BH-2

In the organic light emitting device according to the present invention, a hole transporting layer may be further stacked between the anode and the organic light emitting layer, and an electron transporting layer may be further stacked between the cathode and the organic light emitting layer.

In addition, the hole injection layer may be further laminated on the lower portion of the hole transport layer.

In addition, the electron injection layer may be further stacked on top of the electron transport layer.

According to another embodiment of the present invention, the hole transport layer is N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine ( TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD).

According to a preferred embodiment of the present invention, the hole injection layer may include CuPc, TCTA or m-MTDATA.

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

The blue light emitting compound according to the present invention is characterized in that color purity can be improved by replacing a cyano group with a phenyl substituent of a pyrene derivative . In general, the introduction of various electron-withdrawing groups with high electronegativity improves the color purity, but the efficiency is greatly reduced, making it impossible to use blue light emitting compounds. While maintaining this, there is an advantage that the effect of color purity improvement can be brought.

The organic light emitting display device according to the present invention includes an organic light emitting layer including the blue light emitting compound represented by Chemical Formula 1, an anode and a cathode, and is capable of realizing a full color display because of excellent color purity of the blue light emitting compound. It features.

The organic light emitting display device according to the present invention may further include an anthracene-based host compound represented by Chemical Formula 4 in the organic light emitting layer. When the anthracene-based compound is further included in the emission layer, the pyrene derivative according to the present invention functions as a guest material, and the anthracene-based compound functions as a host material. That is, the light absorption wavelength of the anthracene-based compound is located on the shorter wavelength side than the light absorption wavelength of the pyrene derivative, and since the main emission wavelength of the anthracene-based compound is almost identical to the light absorption wavelength of the pyrene derivative, both are organic light emitting layers When present together, the host material transfers the excitation energy to the guest material and returns to the ground state instead of emitting itself, and only the excited guest material emits the excitation energy as blue light, thereby improving the luminous efficiency of blue light. You have an advantage. In addition, when the light emitting molecules are present alone or in high concentration in the thin film, interaction between the light emitting molecules may occur by approaching the light emitting molecules, and a light emission efficiency degradation phenomenon called concentration quenching may occur, but the host compound may be formed in the organic light emitting layer. When used together, the guest compound may be dispersed at a relatively low concentration, and thus there is an advantage in that the concentration quenching phenomenon can be effectively suppressed.

In the organic light emitting device according to the present invention, a hole transport layer (HTL) is further stacked between the anode and the organic light emitting layer, and an electron transport layer (ETL) is formed between the cathode and the organic light emitting layer. The hole transport layer may be laminated in order to easily inject holes from an anode. As the material of the hole transport layer, electron donating molecules having a small ionization potential are used, mainly triphenylamine. Diamine, triamine or tetraamine derivatives having a basic skeleton thereof are frequently used. The present invention is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl-[1 , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) and the like can be used.

A hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer. The hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc or Starburst type amines listed in Chemical Formula 5, TCTA, m-MTDATA, and the like can be used.

CuPc,

TCTA, m -MTDATA

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention has the opportunity to recombine in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. Serves to increase. The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and, for example, oxadiazole derivatives such as PBD, BMD, BND or Alq ₃ may be used.

Meanwhile, an electron injection layer (EIL) may be further stacked on the upper portion of the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. If it is also commonly used in the art can be used without particular limitation, for example, a material such as LiF, NaCl, CsF, Li ₂ O, BaO and the like can be used.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic light emitting diode according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, a total embroidery layer 60 and a cathode 80, and if necessary, the hole injection layer 30 and The electron injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a method of manufacturing the present invention, as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), and zinc oxide (ZnO) are used as the anode electrode material. The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30. Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and 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. can do. The hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level when the hole is introduced into the cathode through the organic light emitting layer to reduce the lifetime and efficiency of the device. In this case, the hole blocking material used is not particularly limited, but has an ion transporting potential and has a higher ionization potential than the light emitting compound, and BAlq, BCP, TPBI, etc. may be used. After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.

Example 1

1- (1) 1,6- Of dibromopyrene (1,6-dibromopyrene)  synthesis

Pyrene (10 g, 0.049 mol) was added to a three necked round bottom flask and dissolved in CCl ₄ (300 mL), followed by Br ₂ (17.38 g, 0.108 mol) was diluted dropwise with CCl ₄ and slowly added dropwise over 4 hours. After the reaction was completed, the resulting precipitate was filtered as it was, and the precipitate was recrystallized again with toluene to obtain 1,6-dibromopyrene (6.05 g, 34%) white solid.

1- (2) 4- Cyanophenyl Of 4-cyanophenyl phenyl amine  synthesis

4-bromocyanobenzene (20.2 g, 0.11 mol), aniline (12.4 g, 0.13 mol), BINAP (0.7 g, 1% mol), Pd (OAc) ₂ (0.5 g, 2%) in a _two- neck round bottom flask mol) and NaO t Bu (21.3 g, 0.22 mol) were dissolved in toluene (400 mL) and refluxed for 24 hours. After the reaction was terminated, the filtrate was filtered in a hot state, the solid on the funnel was washed with MC and the filtrate was removed toluene and extracted with water and MC. Next, water of the organic layer was removed with MgSO ₄ and separated by column chromatography using Hx: EA (8: 1) as a developing solvent.

1- (3) N, N' - bis (4- cyanophenyl ) -N, N' - diphenylpyrene- 1,6-diamine (N, N' - Bis (4- cyanophenyl) -N, N ' -diphenylpyrene-1,6-diamine) (BD1)

1,6-dibromopyrene (6.9 g, 0.019 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl phenylamine obtained in Example 1- (2) (8.9 g, 0.046 mol), BINAP (0.48 g, 1% mol), Pd (OAc) ₂ (0.13 g, 1% mol) and NaO t Bu (6.4 g, 0.07 mol) were dissolved in toluene (400 mL) It was then refluxed for 24 hours. After the reaction was completed, the mixture was filtered in a hot state, washed with solid MC on the funnel, and then the solvent was removed, and then separated by column chromatography using MC as a developing solvent, and then recrystallized with methanol to give a yellow solid 1.5. g was obtained.

m.p. 353.31 ° C.,

λ ^ABS _max : 408nm λ ^Flu _max : 453 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.19 (d, 2H, J = 9 Hz), 8.09 (d, 2H, J = 9 Hz), 8.11 (d, 2H, J = 9 Hz), 7.85 ( d, 2H, J = 9 Hz), 7.40 (d, 4H, J = 9 Hz), 7.31 (t, 4H, J = 8 Hz), 7.26 (d, 4H, J = 9 Hz), 7.14 (t, 2H, J = 8 Hz), 6.88 (d, 4H, J = 9 Hz))

1- (4) Of organic light emitting device  Produce

After patterning the luminous area of the ITO glass so that it is 3 mm x 3 mm in size, it is cleaned, mounted in a vacuum chamber, the pressure is 1X10 ^-6 torr, and then the organic material is deposited on the ITO glass, CuPC (650 kPa), NPD (400 kPa), An organic light emitting display device was manufactured by forming a film in a sequence of BD1 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) prepared in Example 1- (3). .

Example 2

2- (1) 4- Cyanophenyl Of naphthylamine (4-cyanophenyl naphtylamine)  synthesis

4-bromocyanobenzene (15.3 g, 0.08 mol), 1-naphthylamine (12.0 g, 0.08 mol), BINAP (0.7 g, 1% mol), Pd (OAc) ₂ (0.5) g, 2% mol) and NaO t Bu (21.3 g, 0.22 mol) were dissolved in toluene (300 mL) and refluxed for 24 hours. After the reaction was terminated, the filtrate was filtered in a hot state, the solid on the funnel was washed with MC and the filtrate was removed toluene and extracted with water and MC. Next, water of the organic layer was removed with MgSO ₄ and separated by column chromatography using Hx: EA (10: 1) as a developing solvent.

2- (2) N, N ' - bis (4-cyanophenyl) -N, N' - di-naphthyl pyrene-1,6-diamine (N, N '- Bis (4-cyanophenyl) -N, N '-dinaphtylpyrene-1,6-diamine) synthesis (BD2)

1,6-dibromopyrene (3.9 g, 0.011 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl naphthyl obtained in Example 2- (1) Amine (6.4 g, 0.026 mol), BINAP (0.3 g, 4% mol), Pd (OAc) ₂ (0.1 g, 4% mol) and NaO t Bu (6.4 g, 0.07 mol) were added to toluene (180 mL). After thawing, the mixture was refluxed for 24 hours. After completion of the reaction, the filtrate was filtered in a hot state, the solid on the funnel was washed with MC, the solvent was removed, MC was separated by column chromatography using a developing solvent, and recrystallized with ether to give a yellow solid 0.5. g was obtained.

m.p. 373.7 ° C.,

λ ^ABS _max : 408nm λ ^Flu _max : 450nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.18 (d, 2H, J = 9 Hz), 8.12 (d, 2H, J = 8 Hz), 8.07 (d, 2H, J = 9 Hz), 7.98 ( m, 4H), 7.89 (d, 2H, J = 9 Hz), 7.83 (t, 2H, 6 Hz), 7.55 (t, 2H, J = 8 Hz), 7.50 (m, 2H), 7.42 (d, 4H , J = 6 Hz), 7.38 (d, 4H, J = 9 Hz), 6.62 (m, 4H)

2- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. , An organic light emitting display device was manufactured by forming a film in the order of BD2 (5%) + BH-1 (200Å), Alq3 (350Å), LiF (5Å), and Al (1000Å) manufactured in Example 2- (2). It was.

Example 3

3- (1) 4- Cyanophenyl  Biphenylamine (4- cyanophenyl biphenylamine ) Synthesis

4-bromobiphenyl (30 g, 0.13 mol), 4-aminobenzonitrile (15.2 g, 0.13 mol), BINAP (1.6 g, 2% mol), Pd (OAc) ₂ (0.6 g) in a _two- neck round bottom flask , 2% mol) and NaO t Bu (24.7 g, 0.26 mol) were dissolved in toluene (600 mL) and refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state and the solid on the funnel was washed with MC, and the filtrate was distilled under reduced pressure, and crystals formed by pouring hexane in a small amount of toluene were filtered to obtain 10.6 g of solid.

3- (2) N, N ' - bis (4-cyanophenyl) -N, N' - DB phenyl pyrene-1,6-diamine (N, N '- Bis (4-cyanophenyl) -N, N' -dibiphenylpyrene-1,6-diamine) (BD4)

1,6-dibromopyrene (5.9 g, 0.016 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl biphenyl obtained in Example 3- (1) Amine (10.6 g, 0.039 mol), BINAP (0.41 g, 4% mol), Pd (OAc) ₂ (0.1 g, 3% mol) and NaO t Bu (5.5 g, 0.06 mol) were added to toluene (270 mL). After thawing, the mixture was refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state, washed with solid MC on the funnel, the solvent was removed, and MC was separated by column chromatography using a developing solvent, and then recrystallized with methanol to give 4.8 g of solid. Got it.

m.p. 325.9 ° C.,

λ ^ABS _max : 412nm λ ^Flu _max : 462 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.22 (d, 2H, J = 9 Hz), 8.12 (d, 2H, J = 9 Hz), 8.05 (d, 2H, J = 9 Hz), 7.91 ( d, 2H, J = 9 Hz), 7.55 (m, 8H), 7.42 (m, 8H), 7.35 (d, 2H, J = 9 Hz), 7.30 (m, 4H), 6.95 (d, 4H, J = 9 Hz)

3- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3mm x 3mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1X10 ^-6 torr, the organic material was deposited on the ITO glass, CuPC (650Å), NPD (400Å). , An organic light emitting diode was manufactured by forming a film in the order of BD4 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) prepared in Example 3- (2). It was.

Example 4

Synthesis of 4- (1) 4- cyanophenyl- (2-biphenyl) amine (4- cyanophenyl- (2- bipheny ) lamine )

4-bromobiphenyl (20.2 g, 0.087 mol), 4-aminobenzonitrile (12.5 g, 0.106 mol), DPPF (2.5 g, 5% mol), Pd (OAc) ₂ (5 g) in a _two- neck round bottom flask , 4% mol) and NaO t Bu (17 g, 0.177 mol) were dissolved in toluene (400 mL) and refluxed for 24 hours. After the reaction was completed, the mixture was filtered in a hot state, washed with MC on the funnel, the solvent was removed, MC was separated by column chromatography using a developing solvent, and the crystals formed by adding excess hexane were filtered. 11 g of solid was obtained.

4- (2) N, N' - bis (4- cyanophenyl ) -N, N' - di (2-biphenyl) pyrene- 1,6- diamine (N, N' - Bis (4-cyanophenyl) Synthesis of -N, N'-di (2-biphenyl) pyrene-1,6-diamine) (BD5)

1,6-dibromopyrene (9.85 g, 0.027 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl- (obtained in Example 4- (1) 2-biphenyl) amine (14.8 g, 0.055 mol), BINAP (0.68 g, 4% mol), Pd (OAc) ₂ (0.25 g, 4% mol) and NaO t Bu (10.6 g, 0.11 mol) It was dissolved in (450 mL) and refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state, washed with solid MC on the funnel, the solvent was removed, and MC was separated by column chromatography using a developing solvent, and then recrystallized with hexane to give 1.3 g of solid. Got it.

m.p. 335.84 ° C.,

λ ^ABS _max : 418nm λ ^Flu _max : 453 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ7.93 (d, 2H, J = 8 Hz), 7.65 (d, 2H, J = 9 Hz), 7.58 (d, 2H, J = 8 Hz), 7.55 ( d, 2H, J = 9 Hz), 7.42 (m, 4H), 7.35 (m, 4H), 7.25 (m, 6H), 7.08 (d, 6H, J = 6 Hz), 6.90 (d, 6H, J = 6 Hz)

4- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. , An organic light emitting diode was manufactured by forming a film in the order of BD5 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) prepared in Example 4- (2). It was.

 Example 5

5- (1) 4- Cyanophenyl -(2- Methylphenyl ) Amine (4- cyanophenyl -(2- methylpheny )

lamine ) Synthesis

4-bromobenzonitrile (30 g, 0.165 mol), o-toluidine (17.7 g, 0.1653 mol), BINAP (4.1 g, 4% mol), Pd (OAc) ₂ (0.7 g, 2) in a _two -neck round bottom flask % mol) and NaO t Bu (31.7 g, 0.33 mol) were dissolved in toluene (400 mL) and refluxed for 24 hours. After the reaction was completed, the mixture was filtered in a hot state, washed with MC on the funnel, the solvent was removed, MC was separated by column chromatography using a developing solvent, and the crystals formed by adding excess hexane were filtered. 7.9 g of solid were obtained.

5- (2) N, N' - bis (4- cyanophenyl ) -N, N' - bis (2-methylphenyl) pyrene- 1,6- diamine Synthesis of (N, N'-Bis (4-cyanophenyl) -N, N'-bis (2-methylphenyl) pyrene-1,6-diamine) (BD7)

In a two-neck round bottom flask, 1,6-dibromopyrene (5.7 g, 0.016 mol) prepared in Example 1- (1), 4-cyanophenyl- (obtained in Example 5- (1) 2-methylphenyl) amine (7.9 g, 0.038 mol), BINAP (0.39 g, 1% mol), Pd (OAc) ₂ (0.11 g, 3% mol) and NaO t Bu (5.3 g, 0.06 mol) were added to toluene ( 260 mL) and refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state and the solid on the funnel was washed with MC, the solvent was removed, a small amount of MC was added, ether was added, and the crystals were filtered to obtain 1.7 g of a light green solid.

m.p. 373.1 ° C.,

λ ^ABS _max : 408nm λ ^Flu _max : 450nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.12 (d, 2H, J = 8 Hz), 8.0 (d, 2H, J = 8 Hz), 7.98 (d, 2H, J = 8 Hz), 7.72 ( d, 2H, J = 8 Hz), 7.38 (d, 4H, J = 8 Hz), 7.34 (d, 4H, J = 8 Hz), 7.20 (m, 6H), 6.60 (m, 4H), 2.20 ( s, 6 H)

5- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3mm x 3mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1X10 ^-6 torr, the organic material was deposited on the ITO glass, CuPC (650Å), NPD (400Å). , An organic light emitting diode was manufactured by forming a film in the order of BD7 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) prepared in Example 5- (2). It was.

Example 6

6- (1) 4- Cyanophenyl 4-t-butylphenylamine (4- cyanophenyl -4-t- buthylphenyl

amine ) Synthesis

4-bromobenzonitrile (15 g, 0.08 mol), 4-t-butylbenzene (12.3 g, 0.08 mol), BINAP (1 g, 2% mol), Pd (OAc) ₂ (0.4 in a _two -neck round bottom flask g, 2% mol) and NaO t Bu (15.8 g, 0.16 mol) were dissolved in toluene (300 mL) and refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state and the solid on the funnel was washed with MC, the solvent was distilled off under reduced pressure, extracted with MC and water, and the organic layer was separated. Finally, water of the organic layer was removed with MgSO ₄ , MC was separated by column chromatography using a developing solvent, and recrystallized with methanol to obtain 5.5 g of solid.

6- (2) N, N' - bis (4- cyanophenyl ) -N, N' - bis (4-t-butylphenyl) pyrene- 1,6- diamine Synthesis of (N, N'-Bis (4-cyanophenyl) -N, N'-bis (4-t-buthylphenyl) pyrene-1,6-diamine) (BD9)

1,6-dibromopyrene (3.3 g, 0.009 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl-4 obtained in Example 6- (1) -t-butylphenylamine (5.5 g, 0.022 mol), BINAP (0.23 g, 4% mol), Pd (OAc) ₂ (0.08 g, 4% mol) and NaO t Bu (3.5 g, 0.06 mol) toluene It was dissolved in (150 mL) and refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state, the solid on the funnel was washed with MC, the solvent was removed, a small amount of MC was added, and methanol was added to obtain crystals. Next, using MC as a developing solvent and separated by column chromatography and recrystallized with ether to give a 1.7g of a solid.

m.p. 425.1 ° C.,

λ ^ABS _max : 410nm λ ^Flu _max : 461 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.22 (d, 2H, J = 8 Hz), 8.12 (d, 2H, J = 9 Hz), 8.05 (d, 2H, J = 9 Hz), 7.90 ( d, 2H, J = 8 Hz), 7.42 (d, 2H, J = 8 Hz), 7.35 (d, 4H, J = 8 Hz), 7.22 (d, 4H, J = 8 Hz), 6.88 (d, 4H, J = 8 Hz), 1.30 (s, 18H)

6- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3mm x 3mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1X10 ^-6 torr, the organic material was deposited on the ITO glass, CuPC (650Å), NPD (400Å). , An organic light emitting display device was manufactured by forming a film of BD9 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) in the order of Example 6- (2). It was.

Example 7

7- (1) 4-bromophenyltrimethylsilane (4- bromophenyltrimethylsilane ) Synthesis

Dissolve 1,4-dibromobenzene (12.7 g, 0.053 mol) and diethyl ether (300 ml) in a three-neck round bottom flask, cool the flask to -78 ° C and slowly n-BuLi I dropped it. Next, the temperature was raised to 0 ° C. over 1 hour, and chlorotrimethylsilane (7.51 ml, 0.059 mol) was slowly added dropwise, and the temperature was again raised to room temperature. After completion of the reaction, the mixture was extracted with water and diethyl ether, water was removed with MgSO ₄ , and then the solvent was removed and fractional distillation was performed under reduced pressure to obtain 4-bromophenyltrimethylsilane (11.3 g, 92%).

7- (2) Synthesis of 4-cyano-4-trimethylsilyoxy phenylamine (4-cyanophenyl-4-trimethyl silylphenylamine)

4-cyanophenyl phenylamine (1.2 ml, 0.0076 mol) prepared in Example 1- (2), 4-bromophenyltrimethylsilane prepared in Example 7- (1) in a two-neck round bottom flask (1 g, 0.0044 mol), BINAP (0.03 g, 1% mol), Pd (OAc) ₂ (0.01 g, 1% mol) and NaO t Bu (1.5 g, 0.016 mol) dissolved in toluene (50 mL) It was refluxed for 24 hours. After the reaction was completed, the flask was cooled, the reaction solution toluene was removed, and the column was separated using hexane, and then precipitated using ethanol and water. The precipitate was filtered to give 4-cyanophenyl-4-trimethyl as a white solid. Silylphenylamine (1.12 g, 86%) was obtained.

7- (3) N, N' - bis (4- cyanophenyl ) -N, N' - bis (4-trimethylsilylphenyl) pyrene- 1,6 - diamine (N, N'-Bis (4- cyanophenyl) -N, N'-bis (4-trimethylsilylphenyl) pyrene-1,6-diamine) (BD17)

1,6-dibromopyrene (3.9 g, 0.011 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 4-cyanophenyl-4 obtained in Example 7- (2) -Trimethylsilylphenylamine (6.9 g, 0.026 mol), BINAP (0.27 g, 4% mol), Pd (OAc) ₂ (0.10 g, 4% mol) and NaO t Bu (4.2 g, 0.04 mol) were added to toluene ( 50 mL) and refluxed for 24 hours. After the reaction was completed, the solid on the funnel was washed with MC after filtration in hot state. The MC and toluene were removed under reduced pressure, and methanol was added to obtain crystals, and the crystals were column separated with MC. Finally, the MC was removed under reduced pressure, and then ether was added to a small amount of MC to obtain crystals, followed by recrystallization with MC / MeOH to obtain 2 g of solid.

m.p. 361.8 ° C.,

λ ^ABS _max : 410nm λ ^Flu _max : 456 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.18 (d, 2H, J = 8 Hz), 8.08 (d, 2H, J = 9 Hz), 8.0 (d, 2H, J = 9 Hz), 7.42 ( d, 4H, J = 9 Hz), 7.40 (d, 4H, J = 9 Hz), 7.20 (d, 4H, J = 9 Hz), 6.92 (d, 4H, J = 9 Hz), 0.25 (s, 18H)

7- (4) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. , An organic light emitting diode was manufactured by forming a film of BD17 (5%) + BH-1 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) in the order of Example 7- (3). It was.

Example 8

8- (1) Di-4- Of di-4-cyanophenylamine  synthesis

4-bromobenzonitrile (30 g, 0.16 mol), 4-aminobenzonitrile (19.5 g, 0.16 mol), BINAP (2.0 g, 2% mol), Pd (OAc) ₂ (0.9 g) in a _two -necked round bottom flask , 2% mol) and NaO t Bu (31.7 g, 0.33 mol) were dissolved in toluene (600 mL) and refluxed for 24 hours. After the reaction was completed, the mixture was filtered under hot state, washed with solid MC on the funnel, the solvent was removed, the MC was washed with excess methanol, and the resulting solution was removed under reduced pressure to remove the solvent, and then a small amount of toluene was added. Hexane was poured and recrystallized to give 16.7 g of a beige solid.

Synthesis of 8- (2) N, N, N ' , N' - tetracyanophenylpyrene- 1,6-diamine (N, N, N' , N' - Tetracyano phenylpyrene-1,6-diamine) (BD19 )

1,6-dibromopyrene (5.0 g, 0.014 mol) prepared in Example 1- (1) in a two-neck round bottom flask, di-4-cyanophenyl obtained in Example 8- (1) Amine (7.3 g, 0.033 mol), BINAP (1.73 g, 2% mol), Pd (OAc) ₂ (0.16 g, 1% mol) and NaO t Bu (5.3 g, 0.06 mol) were added to toluene (50 mL). After thawing, the mixture was refluxed for 24 hours. After the reaction was terminated, the mixture was filtered in a hot state and the solid on the funnel was washed with MC and then the solvent was removed and methanol was added to obtain crystals. Next, the solid was separated by column chromatography using MC as a developing solvent, MC was removed under reduced pressure, and a small amount of MC was added to ether to obtain 0.2 g of solid.

m.p. 417.4 ° C.,

λ ^ABS _max : 390nm λ ^Flu _max : 441 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.25 (d, 2H, J = 8 Hz), 8.05 (d, 2H, J = 9 Hz), 7.95 (d, 2H, J = 9 Hz), 7.85 ( d, 2H, J = 8 Hz), 7.52 (d, 8H, J = 8 Hz), 7.12 (d, 8H, J = 8 Hz)

8- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. In Example 8- (2), the BD19 (5%) + BH-1 (200 H), Alq3 (350 Å), LiF (5 Å), Al (1000 Å) to form a film in order to manufacture an organic light emitting device It was.

Example 9

9 (1) Synthesis of 3-cyano-4-trimethylsilyl-phenyl amine (3-cyanophenyl-4-trimethylsilylphenylamine)

3-cyanophenylamine (1.2 ml, 0.0076 mol), 4-bromophenyltrimethylsilane (1 g, 0.0044 mol) prepared in Example 7- (1), BINAP (0.03 g) in a two-neck round bottom flask , 1% mol), Pd (OAc) ₂ (0.01 g, 1% mol) and NaO t Bu (1.5 g, 0.016 mol) were dissolved in toluene (50 mL) and refluxed for 24 hours. After the reaction was completed, the flask was cooled, the reaction solution toluene was removed, extracted with water and MC, water was removed with MgSO ₄ , and MC was removed under reduced pressure. Next, the mixture was subjected to a silica gel short column using hexane, and precipitated using ethanol and water to obtain a white solid.

9- (2) N, N' - bis (3- cyanophenyl ) -N, N' - bis (4-trimethylsilylphenyl) pyrene- 1,6 - diamine (N, N'-Bis (3- cyanophenyl) -N, N'-bis (4-trimethylsilylphenyl) pyrene-1,6-diamine) (BD39)

1,6-dibromopyrene (5.0 g, 0.014 mol) prepared in Example 1- (1) in a two-neck round bottom flask, 3-cyanophenyl-4 obtained in Example 9- (1) Trimethylsilylphenylamine (8.9 g, 0.033 mol), DPPF (0.38 g, 5% mol), Pd (PPh ₃ ) ₄ (0.80 g, 5% mol) and NaO t Bu (4 g, 0.04 mol) It was dissolved in (100 mL) and refluxed for 24 hours. After completion of the reaction, EA: Hx (1: 8) was used as a developing solvent and separated by column chromatography, and recrystallized with methanol to obtain 1.4g of solid.

m.p. 282.0 ° C.,

λ ^ABS _max : 412nm λ ^Flu _max : 455 nm,

¹ H NMR (500 MHz, CDCl ₃ ) δ8.18 (d, 2H, J = 8 Hz), 8.08 (d, 2H, J = 9 Hz), 7.98 (d, 2H, J = 9 Hz), 7.84 ( d, 2H, J = 8 Hz), 7.42 (d, 4H, J = 8 Hz), 7.22 (m, 6H), 7.15 (d, 2H, J = 8 Hz), 7.12 (d, 4H, J = 8 Hz), 0.25 (s, 18H)

9- (3) Of organic light emitting device  Produce

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. , An organic light emitting diode was manufactured by forming a film in the order of BD39 (5%) + BH-2 (200kV), Alq3 (350kV), LiF (5kV), and Al (1000kV) manufactured in Example 9- (2). It was.

Comparative Example 1

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. To form an organic light emitting device was formed by the compound of Formula 6 (5%) + BH-2 (200 Å), Alq3 (350 Å), LiF (5 Å), Al (1000 Å) in order.

Comparative Example 2

After patterning the light emitting area of the ITO glass to a size of 3 mm X 3 mm, washing it, mounting it in a vacuum chamber, and then adjusting the pressure to 1 × 10 ^-6 torr. , A compound of Formula 7 (5%) + BH-1 (200 Pa), An organic light emitting display device was fabricated by forming Alq 3 (350 kV), LiF (5 kV), and Al (1000 kV) in this order.

Test Example 1

For the organic light emitting diodes manufactured according to Examples 1 to 9 and Comparative Examples 1 and 2, voltage, current, brightness, and color coordinates were measured, and the results are shown in Table 1 below.

Voltage (V) Current (mA) Luminance (cd / m ² ) CIE (X) CIE (Y) Example 1 4.9 0.9 580 0.14 0.11 Example 2 5.4 0.9 620 0.15 0.12 Example 3 5.3 0.9 800 0.15 0.17 Example 4 5.1 0.9 600 0.14 0.12 Example 5 5.2 0.9 670 0.14 0.12 Example 6 4.5 0.9 830 0.15 0.16 Example 7 4.9 0.9 580 0.14 0.11 Example 8 5.2 0.9 410 0.13 0.12 Example 9 5.1 0.9 610 0.14 0.12 Comparative Example 1 5.4 0.9 550 0.15 0.21 Comparative Example 2 5.2 0.9 630 0.15 0.20

As can be seen from the results of the above test example, the organic light emitting display device according to the present invention has a color purity higher than that of the conventional blue light emitting compound, but has the same or superior level of brightness as compared with the conventional light emitting compound. It can be seen that it can be usefully used for color displays.

As described above, the organic light emitting display device according to the present invention can be usefully used for full color display because it has excellent color purity of blue without decreasing luminance.

Claims (10)

A blue light emitting compound of Formula 1 below.

(One) Wherein Ar ₁ and Ar ₂ are each

or

ego A ₁ and A ₂ each represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted carbon atom 4 Heteroaryl group containing -19 N, S, O, The said substituent is a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkylamino group, a C1-C10 alkylsilyl, respectively Group, a C6-C14 aryl group, a C4-C19 N, S, O heteroaryl group, cyano group, or halogen.) The method of claim 1, wherein the blue light emitting compound is selected from the group represented by the following formula (2)

,

             BD1 BD2

,

            BD3 BD4

,

             BD5 BD6

,

             BD7 BD8

,

             BD9 BD10

,

            BD11 BD12

,

            BD13 BD14

,

            BD15 BD16

,

            BD17 BD18

,

            BD19 BD20

,

            BD21 BD22

,

            BD23 BD24

,

            BD25 BD26

,

            BD27 BD28

,

            BD29 BD30

,

            BD31 BD32

,

            BD33 BD34

,

            BD35 BD36

,

            BD37 BD38

,

            BD39 BD40

,

           BD41 BD42 (2) The blue light emitting compound of claim 1, wherein the blue light emitting compound is any one selected from the group represented by the following Equation 3.

,

           BD1 BD2

,

           BD7 BD9

,

           BD17 BD39 (3) An organic light emitting device comprising an anode, an organic light emitting layer, and a cathode, wherein the organic light emitting layer comprises a blue light emitting compound according to any one of claims 1 to 3. The organic light emitting device of claim 4, wherein the organic light emitting layer further comprises a compound of Formula 4 as a host compound.

or

(4)  The organic light emitting device of claim 4, wherein a hole transporting layer is further stacked between the anode and the organic light emitting layer, and an electron transporting layer is further stacked between the cathode and the organic light emitting layer. Electroluminescent element. The organic light emitting device of claim 6, wherein a hole injection layer is further stacked below the hole transport layer.        The organic light emitting device of claim 6, wherein an electron injection layer is further stacked on the electron transport layer.        The method of claim 6, wherein the hole transport layer is N, N'-bis (3-methylphenyl) -N, N'-diphenyl-[1,1-biphenyl] -4,4'- diamine (TPD) or, An organic electroluminescent device comprising N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD). The organic light emitting device of claim 7, wherein the hole injection layer comprises CuPc, TCTA, or m-MTDATA.

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