KR100722764B1 - Organic Light Emitting Material and OLED Using The same - Google Patents

Abstract

The present invention relates to a compound derivative used in an organic light emitting diode (OLED) and to an organic light emitting diode using the same, and more particularly, to prepare a triphenylene compound derivative of Formula 1 having a high glass transition temperature and to form a hole of the organic light emitting diode The present invention provides an organic light emitting diode having excellent thermal stability and device lifetime, and excellent light emission luminance and light emission efficiency.

 [Formula 1]

(In Formula 1, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.)

Organic, light emitting, diode, display, hole transport material, triphenylene

Description

Organic Light Emitting Material and OLED Using The same

1 is a UV / Vis for the triphenylene derivative of formula 31 according to the present invention. And fluorescence (PL) spectral graphs.

Figure 2 is a UV / Vis for the triphenylene derivative of formula 35 according to the present invention. And fluorescence spectral graphs.

3 is a differential scanning calorimetry (DSC) curve graph of the triphenylene derivative of Chemical Formula 31 according to the present invention.

4 is a differential scanning calorimeter curve graph of the triphenylene derivative of Chemical Formula 35 according to the present invention.

5 is a thermogravimetric analyzer (TGA) curve graph of the triphenylene derivative of Chemical Formula 31 according to the present invention.

6 is a thermogravimetric curve graph of the triphenylene derivative of Chemical Formula 35 according to the present invention.

7 is a diagram illustrating a multilayer structure of an organic light emitting diode manufactured using the triphenylene derivative according to the present invention.

8 is an electroluminescence (EL) spectrum graph of an organic light emitting diode manufactured using the triphenylene derivative according to the present invention.

The present invention relates to a compound derivative used in an organic light emitting diode (OLED) and an organic light emitting diode using the same, and more particularly, to prepare a compound of Formula 1, which is a triphenylene derivative having a high glass transition temperature and It is used as a hole transport material to provide excellent thermal stability and lifespan of an element, and to provide an organic light emitting diode having excellent luminous brightness and luminous efficiency. Specific examples of the hole transport material are a hole injection layer (HIL) and a hole transport layer (HTL), and in some cases may be an emission layer (EML).

 [Formula 1]

(In Formula 1, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.)

Organic light-emitting diodes (OLEDs), which have several advantages such as low voltage driving, self-luminous, light weight, wide viewing angle, and fast response time, are one of the most active research areas in recent years as one of the next generation flat panel displays to replace LCD. .

In US Pat. No. 4,356,429, Tang discloses a two-layered organic light emitting diode wherein the organic light emitting medium comprises two organic layers sandwiched between an anode and a cathode. That is, the hole transport layer adjacent to the anode contains a hole transport material and has a function of transferring only holes to the light emitting layer mainly in the organic light emitting diode device. Similarly, the electron transport layer adjacent to the cathode contains an electron transport material, and the organic light emitting diode device having a two-layer structure selected to mainly transmit only electrons in the organic light emitting diode device achieves high luminous efficiency, and thus a large part of the technology of the organic light emitting diode. Improved. Therefore, in terms of luminous efficiency, it is a multilayer structure such as a hole transport layer such as a hole injection layer and a hole transporting layer, an electron transporting layer, a hole blocking layer, and the like. Without the system, it is impossible to expect high efficiency and high luminance emission characteristics.

In order to make the organic light emitting diode device practical, in addition to configuring the device in the above multilayer structure, the device material, especially the hole transport material, must have thermal and electrical stability. Because of the heat generated by the device when the voltage is applied, molecules with low thermal stability have low crystal stability, resulting in rearrangement. Finally, if localization occurs and an inhomogeneous part exists, the electric field concentrates on this part. This is because it is accepted to bring about deterioration and destruction of the device. Therefore, the organic layer is usually used in an amorphous state. Moreover, since the organic light emitting diode is a current injection type device, if the material used has a low glass transition temperature (Tg), the heat generated during use causes the organic light emitting diode to deteriorate and shorten the life of the device. . In this respect, materials having a high glass transition temperature are preferred.

Representative examples of the hole-transfer materials used in the prior art include CuPC [copper phthalocyanine] of Formula 2, m-MTDATA [4,4 ′, 4 ”-tris of Formula 3 below ( N- 3-methylphenyl- N -phenylamino) -Triphenylamine, 2-TNATA [4,4 ', 4 "-tris ( N- (niphthylene-2-yl) -N -phenylamino) -triphenylamine] of Formula 4, TPD of Formula 5 [ N, N' -diphenyl- N, N' -di (3-methylphenyl) -4,4'-diaminobiphenyl and NPB of the formula ( N) [ N, N' -di (naphthalen-1-yl) N, N' -diphenylbenzidine].

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6]

Since CuPC is a metal complex compound, it is widely used because it has excellent adhesion to ITO substrate and is the most stable. However, since absorption occurs in the visible light region, it is difficult to realize a total color, and m-MTDATA or 2-TNATA have a glass transition temperature of 78 Not only low as ℃ and 108 ℃ but also a lot of problems in the process of mass production, there is also a problem in realizing the total color. In addition, TPD or NPB also has a fatal disadvantage that the glass transition temperature (Tg) is low as 60 ℃ and 96 ℃, respectively, shorten the life of the device for the same reason.

As described above, the hole transport material used in the conventional organic light emitting diode still contains many problems, and there is a demand for improved performance having excellent physical properties. Therefore, there is an urgent need for development of an excellent material having an improved luminous efficiency of an organic light emitting diode and having high thermal stability and high glass transition temperature.

The present invention is a result obtained by the inventors intensively studied to solve the above problems of the prior art, an object of the present invention to provide a novel organic light emitting diode material.

It is still another object of the present invention to provide a hole transport material for an organic light emitting diode having excellent thermal stability and a method of manufacturing the same, which can improve the luminous efficiency of an organic light emitting diode and increase the lifetime of the device. Another object of the present invention is to provide an organic light emitting diode exhibiting high luminous efficiency. Another object of the present invention is to provide an organic light emitting diode having an extended lifetime. In the present invention, the hole transport material refers to a material used for the hole injection layer or the hole transport layer, and in some cases may be a material used for the light emitting layer.

The present invention relates to a triphenylene derivative represented by Formula 1 below, which is useful as a hole transporting material in an organic light emitting diode. Since the derivatives having the structure of Formula 1 below have a high glass transition temperature (145 ° C or higher) Using this as a hole transport material to produce an organic light emitting diode can increase the luminous efficiency and increase the life of the device.

[Formula 1]

(In Formula 1, R1 or R2 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms. Examples of the aryl group having 6 to 14 nuclear carbon atoms include a phenyl group, a biphenyl group, and a nap. And tilyl, phenanthryl, and anthryl groups.)

A process for preparing the triphenylene derivative according to the present invention will be described below. First, the present inventors synthesized bis (4-halophenyl) acetylene of the following Chemical Formula 7 from benzene substituted with two different halo atoms at 1- and 4- positions by the synthetic route as in Scheme 1 below.

Scheme 1

In Scheme 1, X ₁ or X ₂ is a halogen atom and X ₂ corresponds to a higher period on the periodic table than X ₁ , preferably X ₁ represents a bromine atom or a chlorine atom, and X ₂ represents an iodine atom or a bromine atom. TEA = triethylamine)

[Formula 7] [Formula 8]

(In Formula 7, X ₁ is a halogen atom, preferably a bromine atom or a chlorine atom.)

In addition, the bis (4-bromophenyl) acetylene of the formula (7) and the phencyclone (phencyclone) of the formula (8) reflux in a xylene solvent without a special catalyst to prepare a triphenylene derivative according to the present invention To prepare a dihalo compound of the formula (9). Herein, triphenylene derivatives useful as hole transport materials of organic light emitting diodes were finally prepared through an amination reaction using the dihalo compound represented by Chemical Formula 9 and various secondary amines.

[Formula 9]

(In Formula 9, X ₁ is a halogen atom, preferably a bromine atom or a chlorine atom.)

There are two methods for preparing the hole transport material of the triphenylene derivative which enables the organic light emitting diode of high luminous efficiency and long life from the dihalo compound of Formula 9, as shown in Scheme 2 below.

Scheme 2

The first method represents a dihalo compound of Formula 9 and R 1 -NH ₂ , wherein R 1 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms, as shown in the upper route of Scheme 2. Through the amination reaction of the primary amine represented by.) Was synthesized a compound of the formula (10) which is a secondary amine.

[Formula 10]

(In Formula 10, R1 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms.)

Subsequently, the secondary amine of Formula 10 is reacted with a tertiary amine compound of Formula 11, wherein a halogen atom is substituted with a phenyl group, to finally synthesize triphenylene derivative of Formula 1 according to the present invention.

[Formula 11]

(In Formula 11, X ₃ represents a halogen atom, R 2 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms.)

The second method is a primary amine represented by R 1 -NH ₂ (wherein R 1 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted), as shown in the lower path of Scheme 2 above. Reacting with a tertiary amine of the formula (11) to synthesize a diamine compound of formula (12) first, and then reacting the diamine compound with the dihalo compound of formula (9) to finally obtain a triphenylene derivative of formula (1) according to the present invention It is a method of synthesis.

[Formula 12]

(In Formula 12, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.)

On the other hand, there are two methods for the amination reaction used in each step in order to produce a hole transport material useful for high-performance organic light emitting diodes in the above manner.

The first method is the Ulnamm reaction using a copper catalyst. Although not particularly limited, copper powder or copper sulfate (CuSO ₄ ) is suitable for the reaction, and the reaction base is potassium carbonate or sodium carbonate. Suitable, reaction solvents are N or N -dimethylsulfoxide, nitrobenzene or decalin, which are not used or have a high boiling point. Crown ether or poly (ethylene glycol) may be used to perform the reaction more smoothly.

The second method is a method using a palladium catalyst, which performs an amination reaction using a palladium catalyst, a phosphine catalyst and a base under a suitable reaction solvent. The palladium catalyst used in the reaction is not particularly limited but is mainly palladium acetate or tris (Dibenzylideneacetone) dipalladium (0) is used, and the phosphine catalyst is not particularly limited, but is tri- ( o -tolyl) phosphine, 2,2'-bis (diphenylphosphino) -1,1 '-Binafyl, tri- (n-butyl) phosphine or tri- (t-butyl) phosphine and the like are used. As the reaction base, metal alkoxides such as sodium t-butoxide or potassium th-butoxide are used. The reaction solvent is not particularly limited and may be non-reactive with the reagents used and have a solubility that allows the reaction to proceed smoothly. Specific examples include benzene, toluene, xylene, N, N -dimethylformamide, N, N -dimethylsulfoxide , and the like. The reagent or reaction solvent used in the reaction is not particularly limited thereto.

Specific examples of Chemical Formula 12 used in the amination reaction include compounds represented by the following Chemical Formulas 13 to 30.

[Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

Specific examples of the hole transport material that finally enables the organic light emitting diode having high luminous efficiency and long life through the amination reaction include compounds represented by the following Chemical Formulas 31 to 48. However, the present invention is not limited to these.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

The triphenylene derivative of Formula 1 according to the present invention can be prepared by the same method as described above, and when used as a hole transporting material of an organic light emitting diode, high luminous efficiency can be obtained and the glass transition temperature is high. The element which has can be manufactured. Here, the hole transport material refers to a material used for the hole injection layer, the hole transport layer, and sometimes the light emitting layer. Since the compound of Formula 1 may be used as a hole transport material regardless of the light emitting color of the light emitting material used in the light emitting layer, that is, blue, green or red, the compound of Formula 1 may be effectively used to manufacture a display device having a total color of color and has high durability. It is possible to manufacture a full color display device.

[Formula 1]

(In Formula 1, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.)

For the triphenylene derivatives represented by Chemical Formula 1 of the present invention synthesized as described above, purification was performed using recrystallization and sublimation in view of the characteristics of organic light emitting diodes requiring high purity. Detailed description of the synthesis is described in the synthesis examples below. The physical and photochemical properties of the compounds represented by Formula 31 and Formula 35 prepared through such purification are shown in Table 1 below.

TABLE 1

  compound UV λ _max (nm)  PL (nm)  mp (℃)  Tg (℃)  Td (℃)  Formula 31  349  503  318  151  501  Formula 35  383  494  277  172  506

(The abbreviations used in Table 1 are as follows: UV = ultraviolet absorption, PL = photoluminescence, mp = melting point, Tg = glass transition temperature, Td = decomposition point (1% weight loss temperature))

In order to confirm the optical properties, the UV maximum absorption wavelengths (λ _max ) of the compounds of Chemical Formula 31 and Chemical Formula 35 were measured, respectively, of 349 nm and 383 nm, respectively. Respectively.

Using the maximum absorption wavelength as the excitation wavelength, photoluminescence (PL) spectra were measured for each of the compound of Formula 31 and the compound of Formula 35, and the maximum peaks were measured at 503 nm and 494 nm. In Figure 1 UV / Vis for the compound of formula 31. And fluorescence spectrum measurement results, in Figure 2 UV / Vis for the compound of Formula 35. And the fluorescence spectrum measurement results were shown, which can be seen that the blue to cyan light emission.

In addition, it was measured using a differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA) to confirm the thermal stability for each material. As a result of differential scanning calorimetry, the melting point of the compound of Formula 31 and Formula 35 was 318 ° C and 277 ° C, respectively, and the glass transition temperatures were observed at 150 ° C or higher at 151 ° C and 172 ° C, respectively. Therefore, 2-TNATA [4,4 ', 4' '-tris (N- (naphthylene-2-yl) -N-phenylamino), which has a relatively high glass transition temperature, has been used as a conventional hole transport material. -Triphenylamine] has a significantly higher glass transition temperature, so it has excellent thermal stability, and if applied to the device, it is possible to manufacture a long-life element. The results of the differential scanning calorimetry of the compound of Formula 31 and the compound of Formula 35 are shown in FIGS. 3 and 4.

As a result of thermogravimetric analysis (TGA), a weight loss of 1% of the compound of Formula 31 and Formula 35 was observed at 501 ° C and 506 ° C, respectively. Therefore, since it has thermal stability even at high temperature, there is no risk of decomposition during vacuum deposition in the device manufacturing process, thus an effective device can be manufactured. Thermogravimetric analysis results for the compound of Formula 31 and the compound of Formula 35 are shown in FIGS. 5 and 6.

On the other hand, using the hole transport material according to the present invention as described above to produce an organic light emitting diode as shown in the following example, the results of measuring the electroluminescent properties are shown in Table 2 below. Table 2 shows the results of Examples 1 to 5 and Comparative Example 1 for an organic light emitting diode using Alq ₃ [Tris (8-hydroxyquinoline) aluminum (III)] represented by the following Chemical Formula 48 as a light emitting layer material. will be.

[Formula 48]

TABLE 2

 Hole injection layer  Layer thickness  Applied voltage (V) Current density (mA / cm ² ) Luminance (cd / m ² ) Highest brightness (cd / m ² )  Luminous Efficiency (lm / W)  Luminous Efficiency (cd / A)  Example 1  Formula 31  600  8  5.39  174  25570  1.27  3.23  Example 2  Formula 35  300  8  31.83  968  18780  1.19  3.04  Example 3  Formula 35  400  8  33.02  1167  26820  1.39  3.53  Example 4  Formula 35  500  8  15.00  465  25950  1.22  3.10  Example 5  Formula 35  600  8  5.44  147  21140  1.06  2.71  Comparative Example 1  2-TNATA  600  8  0.52  1.74  15780  0.13  0.33

Table 2 shows an organic light emitting diode using Alq ₃ as the material of the light emitting layer and using the compound of Formula 31 and the compound of Formula 35 as a hole transport material, specifically, a hole injection layer at an applied voltage of 8V. It is the result of measuring light emission characteristic. The compound of Formula 35 is prepared in different thicknesses of 300 Å (Example 2), 400 Å (Example 3), 500 Å (Example 4) and 600 Å (Example 5), respectively. The device was fabricated at 600 Hz to examine the light emission characteristics (Example 1, Comparative Example 1). In the case of using the compound of Formula 31 and the compound of Formula 35 as the hole transporting material, the luminescent properties were excellent in all aspects of current density, brightness, highest brightness, and luminous efficiency than 2-TNATA, a comparative material, regardless of the deposition thickness. Compounds of formula (31) exhibited better luminescence properties than compounds of formula (35) at the same 600 microsecond thickness, and when the compounds of formula 35 were deposited at 400 microseconds (Example 3), they showed the best luminescent properties. .

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. The invention can be better understood by the following synthesis examples, examples and comparative examples, the following synthesis examples and examples are intended to illustrate the invention and the scope of protection defined by the appended claims It is not intended to be limiting.

Synthesis Example 1

Preparation of (4-bromo-phenylethynyl) -trimethyl-silane

Into a 250-ml, three-necked round bottom flask, 50 g (0.177 mol) of 1-bromo-4-iodobenzene was added under a nitrogen atmosphere and diluted with 500 ml of tetrahydrofuran. 54.3 ml (0.389 mol) of triphenylamine, 1.68 g (8.84 mmol) of copper (I) iodide, 2.46 g (3.50 mmol) of dichlorobis (triphenylphosphine) palladium (II) and 25 ml of trimethylsilylacetylene (0.177 mol) was added and refluxed for 1 day. The reaction solution was poured into a saturated aqueous ammonium chloride solution and extracted with dichloromethane. The separated organic layer was washed successively with saturated aqueous ammonium chloride solution and distilled water and dried over magnesium sulfate. This organic layer was concentrated under reduced pressure to obtain 40.8 g of a white target compound (yield 91%).

¹ H NMR (CDCl ₃ ): δ 7.44 (d, J = 8.5 Hz, 2H), 7.32 (d, J = 8.5 Hz, 2H), 0.26 (s, 9H).

The synthetic route of (4-bromo-phenylethynyl) -trimethyl-silane is shown in Scheme 3 below.

Scheme 3

Synthesis Example 2

Other Preparations of (4-Bromo-phenylethynyl) -trimethyl-silane

Into a 250-ml, three-necked round bottom flask, 50 g (0.177 mol) of 1-bromo-4-iodobenzene was added under a nitrogen atmosphere and diluted with 350 ml of piperidine. 1.68 g (8.84 mmol) of copper (I) iodide, 4.08 g (3.50 mmol) of tetrakis (triphenylphosphine) palladium (0) and 25 ml (0.177 mol) of trimethylsilylacetylene were added to the diluent for 2 hours. Stir at room temperature. The reaction solution was poured into a saturated aqueous ammonium chloride solution and extracted with dichloromethane. The separated organic layer was washed successively with saturated aqueous ammonium chloride solution and distilled water and dried over magnesium sulfate. This organic layer was concentrated under reduced pressure to obtain 44.3 g of a white target compound (yield 99%).

Another synthetic route of (4-bromo-phenylethynyl) -trimethyl-silane is shown in Scheme 4 below.

Scheme 4

Synthesis Example 3

Preparation of 4- (bromo) phenylacetylene

A 250-ml, three-necked round bottom flask was charged with 43 g (0.170 mmol) of (4-bromo-phenylethynyl) -trimethyl-silane prepared above, 160 ml of tetrahydrofuran, 200 ml of methanol, and 45 g of potassium carbonate. After stirring for 1 hour at room temperature, the mixture was filtered to remove insoluble matters, and the filtrate was concentrated under reduced pressure. Distilled water and dichloromethane were added to the concentrated solution, and the organic layer was separated. The separated organic layer was dried and concentrated under reduced pressure again to obtain 30.8 g (yield 94%) of a white target compound.

¹ H NMR (CDCl ₃ ): δ 8.47 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 3.13 (s, 1H).

Synthesis route of 4- (bromo) phenylacetylene is shown in Scheme 5 below.

Scheme 5

Synthesis Example 4

Preparation of bis- (4-bromophenyl) acetylene (one kind of formula 7)

In this synthesis example, bis- (4-bromophenyl) acetylene was prepared, which is the case where halogen atom X ₁ in the formula (7) is a bromine atom.

Into a 250-ml, three-necked round bottom flask, 28 g (0.155 mol) of 4- (bromo) phenylacetylene prepared above was added under a nitrogen atmosphere and diluted with 120 ml of triethylamine. In this diluent, 43.8 g (0.155 mol) of 1-bromo-4-iodobenzene, 1.47 g (7.74 mmol) of copper (I) iodide, and 3.57 g (3.09) of tetrakis (triphenylphosphine) palladium (0) mmol) was added and stirred at room temperature for 2 hours. Methanol was added to the reaction solution, and the obtained crystals were filtered and washed with methanol. This solid was dried in vacuo to give 46.9 g (yield 90%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.50 (d, J = 8.3 Hz, 2H), 7.39 (d, J = 8.2 Hz, 2H).

Synthesis route of bis- (4-bromophenyl) acetylene is shown in Scheme 6 below.

Scheme 6

Synthesis Example 5

Preparation of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene (one of formula 9)

In a 500-ml, three-necked round bottom flask, 40 g (0.105 mol) of phencyclone was diluted with 350 ml of o-xylene under nitrogen atmosphere and 37.2 g (0.110 mol) of bis- (4-bromophenyl) acetylene prepared above. ) Was added. The mixture was refluxed for 16 hours, cooled to room temperature and the o-xylene was concentrated under reduced pressure. If about 40 ml of o-xylene remains, stop concentrating and cool to room temperature again. 2000 ml of methanol was thrown into this concentrate, and solid was deposited. The precipitated solid was filtered, washed with methanol and dried in vacuo to give 66.4 g (yield 92%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 8.41 (d, J = 7.8 Hz, 2H), 7.56 (d, J = 7.9 Hz, 2H), 7.40 (t, J = 8.0 Hz, 2H), 7.14-7.09 (m , 6H), 7.06 (d, J = 6.8 Hz, 4H), 7.03-7.00 (m, 6H), 6.54 (d, J = 6.8 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C42H26Br2: 689.2557 (689.0401)

The synthetic route of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene (one type of Formula 9) is shown in Scheme 7 below.

Scheme 7

Synthesis Example 6

Preparation of 4-bromotriphenylamine

In the present synthesis example, in the general formula represented by Formula 11, R2 is a phenyl group and halogen atom X ₃ is a bromine atom.

After 5000-ml and 4-necked round bottom flask was completely dried, 300 g (1.77 mol) of diphenylamine was added under a nitrogen atmosphere and dissolved in 3000 ml of anhydrous toluene. In this solution, 651 g (2.30 mol) of 1-bromo-4-iodobenzene, 10.77 g (35.4 mmol) of tri ( o -tolyl) phosphine, and 16.2 g (17.7 g) of tris (dibenzylideneacetone) dipalladium (0) mmol) and 255.7 g (2.66 mol) of sodium t-butoxide. The mixture was refluxed for 1 day, cooled to 40 ° C., 500 ml of toluene and 1000 ml of distilled water were added, and the target compound was extracted. The separated organic layer was dried, concentrated under reduced pressure to about 500 ml of toluene, and then 3000 ml of methanol was added to form a solid. The resulting solid was filtered, washed with methanol and dried in vacuo to give 441.9 g (yield 77%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.33 (d, J = 8.9 Hz, 2H), 7.28-7.25 (m, 4H), 7.08 (d, J = 7.6 Hz, 4H), 7.05 (t, J = 7.4 Hz , 2H), 6.95 (d, J = 8.9 Hz, 2H).

MALDI-TOF mass (M + H ⁺ ): C18H14BrN: 323.9308 (324.0310)

The synthetic route of 4-bromotriphenylamine is shown in Scheme 8 below.

Scheme 8

Synthesis Example 7

Preparation of N, N, N'-triphenyl-benzene-1,4-diamine (Formula 13)

In this synthesis example, R1 and R2 in the general formula represented by Formula 12 are each a phenyl group.

After 500-ml and 3-necked round bottom flasks were completely dried, 20 g (61.7 mmol) of 4-bromotriphenylamine prepared above was added under a nitrogen atmosphere, and the resultant was dissolved with 170 ml of anhydrous toluene. To this solution 6.74 ml (74.0 mmol), tri- ( o -tolyl) phosphine 0.374 mg (1.23 mmol), tris (dibenzylideneacetone) dipalladium (0) 0.565 g (0.617 mmol) and sodium t-butoxide 7.41 g (77.1 mmol) of seed was added. The mixture was stirred at 65 ° C. for 1 hour, cooled to room temperature, filtered through celite and vacuum filtered. 150 ml of toluene and 150 ml of distilled water were added to the filtrate. The organic layer was separated, dried and concentrated, and the resulting crude crystals were recrystallized from ethyl acetate and hexane and dried in vacuo to yield 14.1 g (yield 68%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.14 (s, NH, 1H), 7.26-7.20 (m, 6H), 7.07-7.04 (m, 4H), 6.98-6.63 (m, 8H), 6.80 (t, J = 7.2 Hz, 1H).

MALDI-TOF mass (M + H ⁺ ): C24H20N2: 337.2194 (337.1626)

The synthetic route of N, N, N'-triphenyl-benzene-1,4-diamine is shown in Scheme 9 below.

Scheme 9

Synthesis Example 8

Preparation of N, N-diphenyl-N '-(1-naphthyl) benzene-1,4-diamine (Formula 17)

In the present synthesis example, in the general formula represented by Formula 12, R1 is a 1-naphthyl group and R2 is a phenyl group.

After 1000-ml and three-necked round bottom flasks were completely dried, 50 g (0.154 mol) of 4-bromotriphenylamine prepared above was added under a nitrogen atmosphere and dissolved in 400 ml of anhydrous toluene. To this solution 26.5 g (0.185 mol) of 1-aminonaphthalene, 6.24 g (30.8 mmol) of tri-t-butylphosphine (10% hexane solution), 1.41 g (1.5) of tris (dibenzylideneacetone) dipalladium (0) mmol) and 35.6 g (0.370 mol) of sodium t-butoxide. The mixture was stirred at 75 ° C. for 1 hour, cooled to room temperature, filtered through celite and vacuum filtered. 300 ml of toluene and 300 ml of distilled water were added to the filtrate. The organic layer was separated, dried and concentrated, and the resulting crude crystals were recrystallized from ethyl acetate and hexane and dried in vacuo to give 45.3 g (yield 76%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.24 (s, NH, 1H), 8.22-8.20 (m, 1H), 7.90-7.88 (m, 1H), 7.54-7.49 (m, 3H), 7.40 (t, J = 6.4 Hz, 1H), 7.32 (d, J = 6.2 Hz, 1H), 7.27 (t, J = 6.8 Hz, 4H), 7.09 (d, J = 7.3 Hz, 2H), 7.00-6.95 (m, 8H).

MALDI-TOF mass (M + H ⁺ ): C28H22N2: 387.2134 (387.1783)

The synthetic route of N, N-diphenyl-N '-(1-naphthyl) benzene-1,4-diamine (Formula 17) is shown in Scheme 10 below.

Scheme 10

Synthesis Example 9

Preparation of 2,3-bis- (4- (1-naphthylamino) phenyl) -1,4-diphenyl-triphenylene (one of formula 10)

In the present Synthetic Example, R1 is a 1-naphthyl group in the general formula represented by Formula 10.

After drying the 250-ml, three-neck round bottom flask completely under a nitrogen atmosphere, 8.5 g of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene prepared by Chemical Formula 9 was prepared. (12.3 mmol) was added and dissolved in anhydrous toluene 80 ml. In this solution, 4.23 g (29.5 mmol) of 1-aminonaphthalene, 0.374 mg (1.23 mmol) of tri ( o -tolyl) phosphine, 56 mg (0.062 mmol) of tris (dibenzylideneacetone) dipaldium (0) and sodium t- 2.96 g (30.8 mmol) of butoxide were added. The mixture was refluxed for 6 hours, cooled to room temperature, and 400 ml of methanol was added thereto. The resulting solid was filtered and washed with methanol to give the crude product. The obtained crude product was recrystallized from ethyl acetate and hexane and dried in vacuo to obtain 8.8 g (yield 88%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.55 (d, J = 7.6 Hz, 2H), 8.09 (d, J = 7.4 Hz, 2H), 8.01 (s, 2H), 7.82 (d, J = 7.3 Hz, 2H), 7.53-7.38 (m, 10H), 7.25-7.02 (m, 16H), 6.68 (d, J = 8.5 Hz, 4H), 6.61 (d, J = 8.5 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C62H42N2: 815.4881 (815.3348)

The synthetic route of 2,3-bis- (4- (1-naphthylamino) phenyl) -1,4-diphenyl-triphenylene is shown in Scheme 11 below.

Scheme 11

Synthesis Example 10

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenylene (Formula 31) Manufacture

This synthesis example induces an amination reaction with diamines to 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene (a type of Formula 9) prepared above, As one of the preferred embodiments of the triphenylene derivative represented by the formula (1) according to the present invention, 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) represented by the formula (31) ) -Phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenylene. As a condition of the amination reaction in this synthesis example, the Uulman reaction using a copper catalyst was used.

250-ml, 3-necked round-bottomed flask, 20.0-3 (0.0434 mol) of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene, prepared as described above, 32.2 g (0.0956 mol) of, N, N'-triphenyl-benzene-1,4-diamine, 18.02 g (0.130 mol) of potassium carbonate and 0.414 g (6.5 mmol) of copper powder are added. After heating the reaction vessel for 20 hours at 220 ° C. to 230 ° C., the reaction solution was cooled to 60 ° C. while adding an appropriate amount of N, N -dimethylformamide to prevent the reaction solution from hardening. Tetrahydrofuran was added to the suspension and filtered to remove insoluble matters. The filtrate was concentrated appropriately and excess methanol was added to precipitate the target compound as a solid. The obtained solid was filtered, washed sequentially with distilled water and methanol and dried in vacuo to give 49.1 g (yield 94%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.56 (d, J = 8.1 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.44 (t, J = 7.6 Hz, 2H), 7.23 (t, J = 7.9 Hz, 8H), 7.19-7.14 (m, 10H), 7.09 (t, J = 3.4 Hz, 4H), 7.04 (t, J = 7.6 Hz, 2H), 6.97-6.72 (m, 12H), 6.88 (t, J = 7.6 Hz, 2H), 6.84 (d, J = 8.8 Hz, 4H), 6.80 (d, J = 7.9 Hz, 4H), 6.71 (d, J = 8.8 Hz, 4H), 6.66 ( d, J = 8.5 Hz, 4H), 6.62 (d, J = 8.5 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C90H64N4: 1201.3193 (1201.5131)

EA: C, 89.8741%; H, 5.3 812%; N, 4.7065% (C, 89.97%; H, 5.37%; N, 4.66%)

UV (λ _max ): 349nm

PL: 503nm

Melting Point (mp): 318 ℃

Glass transition temperature (measured by Tg, DSC): 151 ℃

1% weight loss temperature (measured by TGA): 501 ℃

The synthetic route of Formula 31 is shown in Scheme 12 below.

Scheme 12

Synthesis Example 11

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenylene (Formula 31) Other manufacturing

This synthesis example is 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl represented by the formula (31) as in Synthesis Example 10 above ] -1,4-diphenyl-triphenylene is related to one embodiment, but unlike Synthesis Example 10 In this synthesis example, a palladium catalyst was used in place of the copper catalyst in the conditions of the amination reaction.

52.0 g (0.0753 mol) of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene prepared in a 1000-ml, four-necked round bottom flask, N, N, N'-triphenyl-benzene-1,4-diamine 55.7 g (0.166 mol), tris (dibenzylideneacetone) dipalladium (0) 0.345 g (0.377 mmol), tri- ( o -tolyl) phosphine 0.229 g (0.753 mmol), 17.4 g (0.181 mol) of sodium t-butoxide and 420 ml of toluene were added thereto. The reaction solution was refluxed for 6 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 88.7 g (yield 98%) of the title compound.

The synthetic route of Formula 31 is shown in Scheme 13 below.

Scheme 13

Synthesis Example 12

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenylene (Formula 31) Another manufacture of

This synthesis example uses palladium acetate and tri- (t-butyl) phosphine in place of the tris (dibenzylideneacetone) dipalladium (0) and tri- (o-tolyl) phosphine used in Synthesis Example 11 as a reaction catalyst. Except for the use, it was prepared in the same manner as in Synthesis Example 11 to obtain 86.0 g (yield 95%) of the title compound.

Synthesis Example 13

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Preparation of Formula 35)

This synthesis example is prepared by the above-mentioned 2,3-bis- (4- (1-naphthylamino) phenyl) -1,4-diphenyl-triphenylene (a type of Formula 10) and 4-bromotriphenyl One of the preferred embodiments of the triphenylene derivative represented by the formula (1) according to the present invention by carrying out an amination reaction of an amine (one type of formula 11) is 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene. As a condition of the amination reaction in this synthesis example, the Uulman reaction using a copper catalyst was used.

To 35.0 g (0.0429 mol) of 2,3-bis- (4- (1-naphthylamino) phenyl) -1,4-diphenyl-triphenylene prepared in a 250-ml, three-necked round bottom flask, Also, 30.6 g (0.0945 mol) of 4-bromotriphenylamine prepared above, 17.8 g (0.129 mol) of potassium carbonate and 0.409 g (6.4 mmol) of copper powder are added thereto. After heating the reaction vessel for 30 hours at 220 ° C. to 230 ° C., the reaction solution was cooled to 60 ° C. while adding an appropriate amount of N, N -dimethylformamide to prevent the reaction solution from hardening. Tetrahydrofuran was added to the suspension and filtered to remove insoluble matters. The filtrate was concentrated appropriately and excess methanol was added to precipitate the target compound as a solid. The obtained solid was filtered, washed sequentially with distilled water and methanol, and then dried in vacuo to give 49.2 g (yield 88%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.52 (d, J = 8.2 Hz, 2H), 7.91 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.6 Hz, 2H), 7.44-7.39 (m, 6H), 7.26 (t, J = 7.7 Hz, 2H), 7.19 (t, J = 7.7 Hz, 8H), 7.15 to 7.71 (m, 8H), 7.03 to 6.99 (m, 8H), 6.94 to 6.70 (m, 12H), 6.84 (d, J = 8.8 Hz, 4H), 6.68 (d, J = 8.8 Hz , 4H), 6.52 (s, 6H).

MALDI-TOF mass (M + H ⁺ ): C98H68N4: 1301.2830 (1301.5444)

EA: C, 90.5521%; H, 5.30 45%; N, 4.2454% (C, 90.43%; H, 5.27%; N, 4.30%)

UV (λ _max ): 383nm

PL: 494nm

Melting Point (mp): 277 ℃

Glass transition temperature (measured by Tg, DSC): 172 ℃

1% weight loss temperature (measured by TGA): 506 ℃

The synthetic route of Formula 35 is shown in Scheme 14 below.

Scheme 14

Synthesis Example 14

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Other Preparations of Formula 35)

This synthesis example is 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthyl represented by the formula (35) as in synthesis example 13 above Amino) phenyl] -1,4-diphenyl-triphenylene is related to one embodiment of the present invention. Unlike Synthesis Example 13, in this Synthesis Example, a palladium catalyst was used in place of a copper catalyst as a condition for the amination reaction.

To 45.0 g (0.0552 mol) of 2,3-bis- (4- (1-naphthylamino) phenyl) -1,4-diphenyl-triphenylene prepared in a 1000-ml, four-necked round bottom flask, 39.4 g (0.1215 mol) of 4-bromotriphenylamine, tris (dibenzylideneacetone) dipalladium (0) 0.253 g (0.276 mmol), and 0.168 g (0.552) tri- (o-tolyl) phosphine prepared as described above mmol), sodium t-butoxide 12.7 g (0.133 mol) and toluene 400 ml were added. The reaction solution was refluxed for 8 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 64.7 g (yield 90%) of the title compound.

The synthetic route of Formula 35 is shown in Scheme 15 below.

Scheme 15

Synthesis Example 15

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Another Preparation of Formula 35)

This Synthesis Example was prepared in the same manner as in Synthesis Example 14, except that palladium acetate was used instead of the tris (dibenzylideneacetone) dipalladium (0) used in Synthesis Example 14 as a reaction catalyst, to obtain 65.4 g of the target compound (yield). 91%).

Synthesis Example 16

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Another Preparation of Formula 35)

This Synthesis Example was prepared in the same manner as in Synthesis Example 15, except that tri- (t-butyl) phosphine was used instead of the tri- (o-tolyl) phosphine used in Synthesis Example 15 as the reaction catalyst. 66.8 g (93% yield) were obtained.

Synthesis Example 17

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Another Preparation of Formula 35)

This synthesis example is an amination reaction with diamines (Formula 12) to 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene (a type of Formula 9) prepared above. Induced by one of the preferred embodiments of the triphenylene derivative represented by the formula (1) according to the present invention, 2,3-bis- [4- (N- (4- (N ', N') -Diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene. As a condition of the amination reaction in this synthesis example, the Uulman reaction using a copper catalyst was used.

20.0 g (0.0290 mol) of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene prepared as above in a 250-ml, three-necked round bottom flask; 24.6 g (0.0637 mol) of N-diphenyl-N '-(1-naphthyl) benzene-1,4-diamine (Formula 17), 12.0 g (0.087 mol) of potassium carbonate and 0.276 g (4.3 mmol) of copper powder ). After heating the reaction vessel for 26 hours at 220 ° C. to 230 ° C., the reaction solution was cooled to 60 ° C. while adding an appropriate amount of N, N -dimethylformamide to prevent the reaction solution from hardening. Tetrahydrofuran was added to the suspension and filtered to remove insoluble matters. The filtrate was concentrated appropriately and excess methanol was added to precipitate the target compound as a solid. The obtained solid was filtered, washed sequentially with distilled water and methanol, and then dried in vacuo to give 32.1 g (yield 85%) of the title compound.

The synthetic route of Formula 35 is shown in Scheme 16 below.

Scheme 16

Synthesis Example 18

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Another Preparation of Formula 35)

This synthesis example is 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthyl represented by the formula (35) as in synthesis example 17 above Amino) phenyl] -1,4-diphenyl-triphenylene is related to one embodiment, but unlike Synthesis Example 17, in this Synthesis Example, a palladium catalyst was used instead of a copper catalyst in the conditions of the amination reaction.

In a 1000-ml, four-necked round-bottom flask, 22.0 g (0.0319 mol) of 2,3-bis- (4-bromophenyl) -1,4-diphenyl-triphenylene, prepared as described above, 27.1 g (0.0701 mol), N-diphenyl-N '-(1-naphthyl) benzene-1,4-diamine (Formula 17), tris (dibenzylideneacetone) dipalladium (0) 0.146 g (0.159 mmol) ), Tri- (o-tolyl) phosphine 0.097 g (0.319 mmol), sodium t-butoxide 7.35 g (0.077 mol) and 220 ml of toluene were added. The reaction solution was refluxed for 22 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 39.0 g (yield 94%) of the title compound.

The synthetic route of Formula 35 is shown in Scheme 17 below.

Scheme 17

Synthesis Example 19

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Another Preparation of Formula 35)

This synthesis example uses palladium acetate and tri- (t-butyl) phosphine in place of the tris (dibenzylideneacetone) dipalladium (0) and tri- ( o -tolyl) phosphine used in Synthesis Example 18 as a reaction catalyst. Except for the use, the compound was prepared in the same manner as in Synthesis Example 18 to obtain 38.6 g (yield 93%) of the title compound.

Hereinafter, an embodiment of fabricating an organic light emitting diode using the hole transport material of the present invention prepared as described above is shown, and as the material of the light emitting layer Alq ₃ [tris (8-hydroxyquinoline) aluminum (III) of the formula 48 ] Was deposited to a thickness of 500 kPa to form a light emitting layer. As can be seen in Table 2, Example 1 used the triphenylene derivative of Formula 31 as the hole transport material. Examples 2 to 5 used the triphenylene derivative of Formula 35 as the hole transport material, each embodiment is characterized in that produced by varying the thickness of the hole injection layer. In Comparative Example 1, a light emitting layer having a thickness similar to that of Example 1 and Example 5 was produced using 2-TNATA, which is well known in the art.

Example 1

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenylene (Formula 31) Manufacture of Organic Light Emitting Diodes with Thickness of 600Å

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl Triphenylene was deposited to a thickness of 600 kPa to form a hole injection layer. Subsequently, NPB [N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine] of Chemical Formula 6 was deposited to a thickness of 200 GPa to form a hole transport layer. Alq ₃ [tris (8-hydroxyquinoline) aluminum (III)] of formula 48 was deposited to a thickness of 500 GPa to form a light emitting layer. Finally, aluminum and lithium were simultaneously deposited to form a cathode having a thickness of 1000 mW. The light emission test was performed by applying a voltage of 0 to 15V to the organic light emitting diode manufactured as described above. That is, the current density, luminance, luminous efficiency, EL peak, color coordinate, and highest luminance at each voltage were measured. Some of the results are shown in Table 2 below.

[Formula 6] [Formula 48]

Example 2

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Fabrication of Organic Light Emitting Diode having Thickness of 300Å

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] of the formula (35) -Diphenyl-triphenylene was deposited to a thickness of 300 kPa to form a hole injection layer. Subsequently, NPB of Chemical Formula 6 was deposited to have a thickness of 200 μs to form a hole transport layer. Alq ₃ of Formula 48 was deposited to a thickness of 500 kPa to form a light emitting layer. Finally, aluminum and lithium were simultaneously deposited to form a cathode having a thickness of 1000 mW. The light emission test was performed by applying a voltage of 0 to 15V to the organic light emitting diode manufactured as described above. That is, the current density, luminance, luminous efficiency, EL peak, color coordinate, and highest luminance at each voltage were measured. Some of the results are shown in Table 2 below.

Example 3

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Fabrication of Organic Light Emitting Diode having Thickness of Formula 35)

In Example 3, 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl of Chemical Formula 35 in Example 2 was used. ] -1,4-diphenyl-triphenylene was fabricated and evaluated in the same manner as in Example 2 except that the thickness was increased to 400 mW instead of 300 mW. The results are shown in Table 2 below.

Example 4

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Fabrication of Organic Light Emitting Diode with Thickness of 500Å

In Example 4, 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl of Chemical Formula 35 in Example 2 was used. ] -1,4-diphenyl-triphenylene was fabricated and evaluated in the same manner as in Example 2 except that the thickness was increased to 500 mW instead of 300 mW. The results are shown in Table 2 below.

Example 5

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl] -1,4-diphenyl-triphenylene ( Fabrication of Organic Light Emitting Diode with Thickness of 600Å

Example 5 is 2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -1-naphthylamino) phenyl of Chemical Formula 35 in Example 2 ] -1,4-diphenyl-triphenylene was fabricated and evaluated in the same manner as in Example 2 except that the thickness was increased to 600 mW instead of 300 mW. The results are shown in Table 2 below.

Comparative Example 1

2-TNATA [4,4 ', 4 "-tris ( N -(2-naphthyl)- N -Phenylamino) -triphenylamine] organic light emitting diode having a thickness of 600 Hz

In Comparative Example 1, a hole injection layer was manufactured from 2-TNATA, which is well known in the art, in the same thickness (600 Pa) as in Examples 1 and 5.

2,3-bis- [4- (N- (4- (N ', N'-diphenylamino) -phenyl) -phenylamino) phenyl] -1,4-diphenyl-triphenyl of the formula (31) Except for using 2-TNATA [4,4 ', 4 "-tris ( N- (2-naphthyl) -N -phenylamino) -triphenylamine] of Chemical Formula 4 as a hole injection layer instead of ene, An organic light emitting diode was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[Formula 4]

As a result of measuring the light emission characteristics by manufacturing the organic light emitting diode as in the above Example or Comparative Example is shown in Table 2 below, Table 2 is described again below.

TABLE 2

 Hole injection layer  Layer thickness  Applied voltage (V) Current density (mA / cm ² ) Luminance (cd / m ² ) Highest brightness (cd / m ² )  Luminous Efficiency (lm / W)  Luminous Efficiency (cd / A)  Example 1  Formula 31  600  8  5.39  174  25570  1.27  3.23  Example 2  Formula 35  300  8  31.83  968  18780  1.19  3.04  Example 3  Formula 35  400  8  33.02  1167  26820  1.39  3.53  Example 4  Formula 35  500  8  15.00  465  25950  1.22  3.10  Example 5  Formula 35  600  8  5.44  147  21140  1.06  2.71  Comparative Example 1  2-TNATA  600  8  0.52  1.74  15780  0.13  0.33

As the triphenylene derivative according to the present invention, the hole transport material has a high glass transition temperature and a high pyrolysis temperature of 150 ° C. or higher, and thus has excellent thermal stability. Compared to the 2-TNATA of the hole transport material of Formula 4, the luminescent properties were much better in terms of current density, brightness, highest brightness and luminous efficiency. Therefore, when the organic light emitting diode is manufactured by using the triphenylene derivative of the present invention as the hole injection layer, not only the light emitting luminance and the low luminous efficiency, which are the biggest disadvantages of the conventional organic light emitting diode, can be solved at the same time, but also the glass transition Since the temperature is also high, the thermal stability of the organic light emitting diode is excellent, and thus, a high-performance organic light emitting diode can be manufactured, which can greatly contribute to the commercialization of all-color organic light emitting diodes requiring high efficiency, high brightness, and long life. Simple modifications or changes of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be included in the scope of the present invention.

Claims (6)

Triphenylene derivative represented by the following formula (1), characterized in that used as a hole transport material of the organic light emitting diode (OLED). [Formula 1]

(In Formula 1, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.) The triphenylene derivative according to claim 1, wherein the triphenylene derivative represented by the following formula (9) is a dihalo compound represented by the following formula (9) R1-NH ₂ (wherein R1 is an aryl having 6 to 14 nuclear carbon atoms substituted or unsubstituted) To synthesize a compound of formula 10, which is a secondary amine, by reacting with a tertiary amine compound of formula 11 Triphenylene derivative, characterized in that. [Formula 9]

(In Formula 9, X ₁ represents a halogen atom.) [Formula 10]

(In Formula 10, R1 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms.) [Formula 11]

(In Formula 11, X ₃ represents a halogen atom, R 2 represents a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms.) The triphenylene derivative according to claim 1, wherein the triphenylene derivative represented by Chemical Formula 1 is prepared by reacting a dihalo compound represented by Chemical Formula 9 with a diamine compound represented by Chemical Formula 12. [Formula 9]

(In Formula 9, X ₁ represents a halogen atom.) [Formula 12]

(In Formula 12, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.) The triphenylene derivative according to claim 1, wherein the triphenylene derivative represented by Chemical Formula 1 is represented by the following Chemical Formulas 31 to 48 with R1 or R2 specifically specified. [Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

The triphenylene derivative according to claim 3, wherein the diamine compound of Formula 12 is represented by the following Formulas 13 to 30. [Formula 12]

(In Formula 12, R1 or R2 represents an aryl group having 6 to 14 nuclear carbon atoms substituted or unsubstituted.) [Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

An organic light emitting diode comprising the triphenylene derivative according to claim 1 or 4 as a hole injection material, a hole transport material or a light emitting layer material.

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