KR20110054225A - Organic light emitting material and organic light emitting diode having the same - Google Patents

Abstract

PURPOSE: An organic light emitting material is provided to ensure excellent thermal stability, to improve the luminous efficiency of an organic electroluminescent device, and to increase the life span of the device. CONSTITUTION: An organic light emitting material is used as a light emitting material of an organic electroluminescent device and includes a triphenylene derivative represented by chemical formula I. In chemical formula I, R1 and R2 are hydrogen or substituted or unsubstituted aryl group having 6-30 nucleus carbon atoms. The organic electroluminescent device includes one or more organic layers including the organic light emitting material.

Description

Organic electroluminescent composition and organic electroluminescent device comprising same {Organic Light Emitting Material and Organic Light Emitting Diode Having The Same}

The present invention relates to an organic electroluminescent device, and more particularly, to a triphenylene derivative used as a light emitting material of an organic electroluminescent device, and more particularly, to produce a triphenylene derivative and to produce a hole transport material of the organic electroluminescent device. It is used to increase the life of the device, to provide an organic electroluminescent device excellent in light emission luminance and light emission efficiency.

Organic electroluminescent devices with various advantages such as low voltage driving, self-luminous, light weight, wide viewing angle and fast response speed are one of the most researched fields as one of the next generation flat panel displays to replace LCD.

In US Pat. No. 4,356,429, Tang et al. Disclosed a two-layered organic electroluminescent device comprising two organic layers (hole transport layer and light emitting layer) 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 electroluminescent device. Similarly, the electron transport layer adjacent to the cathode contains an electron transport material, and the organic electroluminescent device device having a two-layer structure selected to mainly transmit only electrons within the organic electroluminescent device device achieves high luminous efficiency and thus substantially organic electroluminescence. The technology of the device was improved. Therefore, in terms of luminous efficiency, a multilayer structure including 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 multilayer system, it is impossible to expect high efficiency and high luminance.

In order to realize the organic electroluminescent device device, in addition to configuring the device in the above multilayer structure, the device material, in particular, 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 electroluminescent device 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 electroluminescent device to deteriorate and shorten the life of the device. Let's go. In this respect, materials having a high glass transition temperature are preferred.

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

[Formula 1] [Formula 2]

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 of shortening the life of the device for the same reason because the glass transition temperature (Tg) is low as 60 ℃ and 96 ℃, respectively.

As described above, the hole transport material used in the conventional organic electroluminescent device 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 electroluminescent device and having high thermal stability and high glass transition temperature.

An object of the present invention is to provide a triphenylene compound derivative having a high glass transition temperature, an organic electroluminescent composition comprising the same, and an organic electroluminescent device to solve the above problems. Another object of the present invention is to provide a hole transport material for an organic electroluminescent device having excellent thermal stability and a method of manufacturing the same, which can improve the luminous efficiency of the organic electroluminescent device and increase the lifetime of the device. Still another object of the present invention is to provide an organic electroluminescent device exhibiting high luminous efficiency. Another object of the present invention is to provide an organic electroluminescent device having an extended lifetime.

First, the present invention is an organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device and comprises a triphenylene derivative represented by the following general formula (I).

[Formula I]

(In formula (I), R1 and R2 are each hydrogen or an aryl group having 6 to 30 nuclear carbon atoms substituted or unsubstituted.)

Another embodiment of the present invention is an organic electroluminescent device comprising at least one organic layer comprising the organic light emitting composition described above. Here, the organic electroluminescent device includes an organic light emitting diode, an organic field-effect transistor, an organic thin film transistor, an organic laser diode, an organic solar cell, an organic light emitting electrochemical cell, or an organic integrated circuit. It is apparent to those skilled in the art that various applications such as diodes can be made.

Other embodiments are described in the detailed description and drawings below.

Since the triphenylene derivative according to the present invention has a high glass transition temperature and a high pyrolysis temperature of 130 ° C. or higher, the thermal stability is excellent. As a result, the present invention showed better luminescence properties in terms of current density, luminance, highest luminance, and luminous efficiency than conventional hole transport materials, 2-TNATA (Formula 1) or NPB (Formula 2).

Accordingly, when the organic electroluminescent device is manufactured by using the triphenylene derivative according to the present invention as a hole transporting material, the problem of low luminous brightness and low luminous efficiency, which is the biggest disadvantage of the conventional organic electroluminescent device, is simultaneously solved. In addition to the high glass transition temperature, the thermal stability of the organic electroluminescent device is excellent, making it possible not only to manufacture a high performance organic electroluminescent device but also to commercialize a full-color organic electroluminescent device requiring high efficiency, high brightness and long life. Can contribute significantly.

The present invention is a triphenylene derivative represented by the following general formula (I) which is useful for use as a hole transport material or an organic electroluminescent material in an organic electroluminescent device, and the triphenylene derivative has a high glass transition temperature and excellent hole injection and transport ability. Since the organic electroluminescent device is manufactured using the same as a hole transport material, the light emitting efficiency can be increased and the life of the device can be increased.

[Formula I]

(In formula (I), R1 and R2 are each hydrogen or an aryl group having 6 to 30 nuclear carbon atoms substituted or unsubstituted.)

The present invention may be an organic light emitting composition or an organic light emitting material or a triphenylene derivative which can be used as a light emitting material of the organic electroluminescent device as described above.

In the present invention, an aryl group having 6 to 30 nuclear carbon atoms substituted or unsubstituted is an aryl having 6 to 30 nuclear carbon atoms, which is substituted by a specific functional group or unsubstituted by any functional group. Group, and examples of such aryl groups include phenyl group, naphthyl group, phenanthryl group, anthryl group, biphenyl group, terphenyl group, fluorene group and the like.

In addition, R1 and R2 of Formula I may be connected to each other by a single bond, a methylene group, an ethylene group or a vinyl group to form a fused ring.

Specific examples of the triphenylene derivative having the structure of Formula (I), which specifically enable an organic electroluminescent device having a particularly high luminous efficiency and a long lifetime, include at least one of the compounds represented by the following Chemical Formulas 11 to 23. However, the present invention is not limited to these.

[Formula 11] [Formula 12]

[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]

The present invention may be a material or composition for an organic electroluminescent device comprising the triphenylene derivative as described above. When such a material or composition is used as a hole transporting material of an organic electroluminescent device, high luminous efficiency can be obtained, and a device having excellent durability can be manufactured because the glass transition temperature of the triphenylene derivative is high. Here, the hole transport material refers to a material used for the hole injection layer or the hole transport layer, in some cases may be a material used for the light emitting layer.

In addition, the triphenylene derivatives according to the present invention may be purified using recrystallization and sublimation methods due to the characteristics of the organic electroluminescent device requiring high purity.

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

Example 1 Preparation of Chemical Formula 11

In the present invention, the triphenylene derivative represented by Chemical Formula I may be prepared by a synthetic route as in Scheme 1 below.

Scheme 1

1-1. Preparation of Formula 102

100 g (0.273 mol) of 2,7-dibromophenanthrene-9,10-dione (Formula 101), 58 g of 1,3-diphenylacetone and 5000 ml of ethanol were added to a 10000-ml, 5-neck round bottom flask. I was. 30 g of potassium hydroxide was added to the solution and stirred at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, the resulting solid was filtered and washed well with methanol. The resulting solid was dried in vacuo to give 115 g (yield 78%) of the title compound.

1-2. Preparation of Chemical Formula 103

In a 2000-ml, five-necked round bottom flask, 110 g (0.204 mol) of the compound of formula 102 prepared in Example 1-1 were diluted with 1100 ml of o-xylene and 25 g of trimethylsilylacetylene was added under a nitrogen atmosphere. The mixture was refluxed for 12 hours, cooled to room temperature, and poured into excess methanol to precipitate a solid. The precipitated solid was filtered, washed with methanol and dried in vacuo to give 110 g (yield 88%) of the title compound.

1-3. Preparation of Formula 104

2000-ml, 4-necked round bottom flask, 100 g (0.164 mol) of formula 103 compound prepared in Example 1-2 under nitrogen atmosphere, 800 ml of tetrahydrofuran, 200 ml of tetrabutylammonium fluoride (1M-tetrahydrofuran solution) Was added in sequence. After stirring for 4 hours at room temperature, the mixture was extracted using distilled water and chloroform. The organic layer was separated, concentrated appropriately, and methanol was added to the precipitated solid. The precipitated solid was filtered and dried to obtain 85 g (yield 96%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.20 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 2.0 Hz, 2H), 7.56 (s, 2H), 7.50 (dd, J = 8.8, 2.0 Hz, 2H), 7.45-7.41 (m, 10H).

1-4. Preparation of Formula 11

In a 500-ml, three-necked round bottom flask, nitrogen compound 21 g (0.039 mol) prepared in Example 1-3, diphenylamine 14.5 g, palladium acetate (II) 0.09 g, tri- (t-butyl) ) 1.5 g of phosphine (10% hexane solution), 9 g of sodium t-butoxide and 210 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 27 g (yield 96%) of the title compound.

MS ( m / z , [M] ⁺ ): C 54 H 38 N 2: 714.51 (714.30).

Example 2 Preparation of Chemical Formula 12

500 g, a three-necked round bottom flask was prepared in Example 1-3 under nitrogen atmosphere, 21 g (0.039 mol) of the compound of formula 104, 18 g of N -phenyl-1-naphthylamine, 0.09 g of palladium acetate (II), tri 1.5 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 210 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 26 g (yield 83%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.29 (d, J = 9.2 Hz, 2H), 7.96 (d, J = 8.0 Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.59-7.45 (m, 4H), 7.36 (t, J = 8.0 Hz, 2H), 7.24-6.95 (m, 22H), 6.86 (t, J = 6.8 Hz, 2H), 6.61 (d, J = 8.4 Hz, 4H).

UV (λ _max ): 352 nm PL: 469 nm (see Fig. 1)

Glass transition temperature (measured by Tg, DSC): 151 ° C (see Figure 2)

Example 3 Preparation of Chemical Formula 13

500-ml, 3-necked round bottom flask was prepared in Example 1-3 under nitrogen atmosphere, 21 g (0.039 mol) of formula 104 compound, 18 g of N -phenyl-2-naphthylamine, 0.09 g of palladium acetate (II), tri 1.5 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 210 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 24 g (yield 76%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.25 (d, J = 8.8 Hz, 2H), 7.74 (d, J = 8.8 Hz, 2H), 7.60 (d, J = 8.8 Hz, 2H), 7.54 (d , J = 8.0 Hz, 2H), 7.41-7.33 (m, 6H), 7.29-7.26 (m, 4H), 7.20-7.10 (m, 10H), 7.03 (dd, J = 8.8, 2.0 Hz, 2H), 6.98-6.95 (m, 2H), 6.87-6.82 (m, 8H) 6.73-6.69 (m, 2H).

UV (λ _max ): 368nm PL: 468nm

Glass transition temperature (measured by Tg, DSC): 149 ℃

Example 4 Preparation of Chemical Formula 14

500-ml, 3-necked round bottom flask, 21 g (0.039 mol) of the compound of formula 104 prepared in Example 1-3 under nitrogen atmosphere, 23 g of N -phenyl-9-phenanthrylamine, 0.09 g of palladium acetate (II), tri 1.5 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 210 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 under vacuum to obtain 28 g (yield 78%) of the title compound.

H NMR (400 MHz, CDCl): δ 8.70 (d, J = 8.4 Hz, 4H), 8.24 (s, 2H), 7.80 (d, J = 7.7 Hz, 2H), 7.69-7.56 (m, 8H), 7.38 (t, J = 7.0 Hz, 6H), 7.29-7.20 (m, 2H), 7.12-7.07 (m, 6H), 6.93 (d, J = 6.6 Hz, 4H), 6.83-6.79 (m, 6H), 6.52-6.44 (m, 6 H).

UV (λ _max ): 375 nm PL: 463 nm (see FIG. 3)

Glass transition temperature (measured by Tg, DSC): 188 ° C (see Figure 4)

Example 5 Preparation of Chemical Formula 15

5-1. Preparation of Formula 105

In a 500-ml, three-necked round bottom flask under nitrogen atmosphere, 28 g (0.052 mol) of formula 104 compound prepared in Example 1-3, 11 g of aniline, 0.12 g of palladium acetate (II), tri- (t-butyl) phosphine 2.1 g (10% hexane solution), 12 g of sodium t-butoxide and 280 ml of toluene were added thereto. The reaction solution was refluxed for 4 hours, cooled, and poured into an excess of 90% methanol aqueous solution to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 28 g (yield 96%) of the title compound.

5-2. Preparation of Formula 15

500 g, 25 g (0.044 mol) of formula 105 compound prepared in Example 5-1 in a three-necked round bottom flask under nitrogen atmosphere, 26 g of 2-bromo-9,9-dimethyl-9 H -fluorene, palladium acetate 0.1 g of (II), 1.8 g of tri- (t-butyl) phosphine (10% hexane solution), 10 g of sodium t-butoxide and 250 ml of toluene were added thereto. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 35 g (yield 85%) of the title compound.

MS ( m / z , [M] ⁺ ): C 72 H 54 N 2: 746.59 (946.43).

Example 6 Preparation of Chemical Formula 17

43 g (0.076 mol) of formula 105 compound prepared in Example 5-1, 500 g of 4-bromo- N, N -diphenylaniline, and palladium acetate (II) 0.17 in a 500-ml, three-neck round bottom flask g, tri- (t-butyl) phosphine (10% hexane solution) 3.1 g, sodium t-butoxide 18 g and 400 ml of toluene were added. 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 65 g (yield 81%) of the title compound.

H NMR (400 MHz, DMSO-d ₆ ): δ 8.37 (d, J = 9.2 Hz, 4H), 7.40 (s, 4H), 7.31 (t, J = 7.7 Hz, 8H), 7.26-7.16 (m, 16H ), 7.01 (d, J = 7.3 Hz, 12H), 6.88 (d, J = 8.4 Hz, 4H), 6.76 (d, J = 8.8 Hz, 4H), 6.66 (d, J = 8.8 Hz, 4H).

UV (λ _max ): 374nm PL: 499nm

Glass transition temperature (measured by Tg, DSC): 150 ℃

Example 7 Preparation of Chemical Formula 20

500 g, 3-necked round bottom flask, 21 g (0.039 mol) of formula 104 compound prepared in Example 1-3 under nitrogen atmosphere, 23 g of N- (2-naphthyl) -1-naphthylamine, palladium acetate (II ) 0.09 g, tri- (t-butyl) phosphine (10% hexane solution) 1.5 g, sodium t-butoxide 9 g and 210 ml of toluene were added. 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 28 g (yield 80%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.19 (d, J = 8.8 Hz, 2H), 7.86 (d, J = 8.0 Hz, 2H), 7.74-7.72 (m, 4H), 7.68 (d, J = 7.6 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.44-7.19 (m, 18H), 7.05-6.94 (m, 10H), 6.73-6.71 (m, 6H).

UV (λ _max ): 367nm PL: 464nm

Glass transition temperature (measured by Tg, DSC): 173 ℃

Example 8 Preparation of Chemical Formula 21

500 g, 3-necked round bottom flask, 21 g (0.039 mol) of Formula 104 compound prepared in Example 1-3 under nitrogen atmosphere, 25 g of N- (4-biphenyl) -1-naphthylamine, palladium acetate (II ) 0.09 g, tri- (t-butyl) phosphine (10% hexane solution) 1.5 g, sodium t-butoxide 9 g and 210 ml of toluene were added. 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 afford the desired compound 35 (yield 94%).

H NMR (400 MHz, DMSO-d ₆ ): δ 8.30 (d, J = 8.8 Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.87 (d, J = 8.0 Hz, 2H), 7.62- 7.57 (m, 6H), 7.49-7.34 (m, 16H), 7.29-7.25 (m, 4H), 7.15-7.00 (m, 14H), 6.66 (d, J = 8.8 Hz, 4H).

UV (λ _max ): 366 nm PL: 469 nm (see FIG. 5)

Glass transition temperature (measured by Tg, DSC): 176 ℃

Example 9 Preparation of Chemical Formula 23

9-1. Preparation of Formula 106

In a 500-ml, three-necked round-bottom flask, 45 g (0.083 mol) of formula 104 compound prepared in Example 1-3, 26 g of 1-naphthylamine, 0.19 g of palladium acetate (II), tri- (t- 3.4 g of butyl) phosphine (10% hexane solution), 19 g of sodium t-butoxide and 400 ml of toluene were added thereto. The reaction solution was refluxed for 3 hours, cooled, and poured into an excess of 90% methanol aqueous solution to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 45 g (yield 82%) of the title compound.

9-2. Preparation of Formula 23

51 g (0.076 mol) of formula 106 compound prepared in Example 9-1, 500 g of 4-bromo- N, N -diphenylaniline, palladium acetate (II) 0.17 in a 500-ml, three-necked round bottom flask under nitrogen atmosphere g, tri- (t-butyl) phosphine (10% hexane solution) 3.1 g, sodium t-butoxide 18 g and 400 ml of toluene were added. 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 84 g (yield 96%) of the title compound.

H NMR (400 MHz, DMSO-d ₆ ): δ 8.26 (d, J = 9.2 Hz, 4H), 7.97 (d, J = 8.4 Hz, 4H), 7.85 (d, J = 7.6 Hz, 4H), 7.40 ( d, J = 8.4 Hz, 4H), 7.52-7.38 (m, 8H), 7.30-7.24 (m, 10H), 7.12-6.96 (m, 18H), 6.84 (d, J = 9.2 Hz, 4H), 6.63 (d, J = 8 Hz, 4H).

UV (λ _max ): 375nm PL: 435nm

Glass transition temperature (measured by Tg, DSC): 192 ℃

Example 10 Preparation of Chemical Formula 24

25 g (0.037 mol) of formula 106 compound prepared in Example 9-1, 26 g of 9- (4-bromophenyl) -9 H -carbazole and 500 palladium acetate II) 0.08 g, tri- (t-butyl) phosphine (10% hexane solution) 1.5 g, sodium t-butoxide 9 g and 220 ml of toluene were added. The reaction solution was refluxed for 7 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 31 g (yield 75%) of the title compound.

MS ( m / z , [M] ⁺ ): C 86 H 56 N 4: 1144.58 (1144.45).

Example 11 Preparation of Chemical Formula 25

500-ml, 3-necked round bottom flask, 21 g (0.039 mol) of formula 104 compound prepared in Example 1-3, 23 g of di- (2-naphthyl) amine, 0.09 g of palladium acetate (II) 1.5 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 210 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 33 g (yield 92%) of the title compound.

H NMR (400 MHz, CDCl): δ 8.30 (d, J = 8.8 Hz, 2H), 7.76 (d, J = 8.8 Hz, 4H), 7.63 (d, J = 9.2 Hz, 4H), 7.53 (d, J = 8.0 Hz, 4H), 7.46-7.32 (m, 10H), 7.24-7.21 (m, 6H), 7.18-7.17 (m, 4H), 7.10-7.06 (m, 6H), 6.66 (t, J = 8.0 Hz, 4H), 6.44 (t, J = 7.6 Hz, 2H).

UV (λ _max ): 363 nm PL: 465 nm (see FIG. 6)

Glass transition temperature (measured by Tg, DSC): 192 ℃

Example 12 Preparation of Chemical Formula 26

500 g, 25-g (0.046 mol) of the compound of formula 104 prepared in Example 1-3 in a three-necked round bottom flask under nitrogen atmosphere, 32 g of di- (4-biphenyl) amine, 0.10 g of palladium acetate (II), tri 1.9 g of-(t-butyl) phosphine (10% hexane solution), 11 g of sodium t-butoxide and 250 ml of toluene o-xylene were added. The reaction solution was refluxed for 10 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 36 g (yield 76%) of the title compound.

H NMR (400 MHz, DMSO-d ₆ ): δ 8.16 (d, J = 8 Hz, 4H), 7.81 (d, J = 8 Hz, 4H), 7.69 (d, J = 8 Hz, 4H), 7.57-7.48 (m , 8H), 7.42-7.26 (m, 12H), 7.19-7.16 (m, 10H), 7.01-6.93 (m, 8H), 6.62 (d, J = 8.8 Hz, 4H).

UV (λ _max ): 357nm PL: 472nm

Glass transition temperature (measured by Tg, DSC): 190 ℃

Example 13 Preparation of Chemical Formula 27

In a 500-ml, three-necked round bottom flask under nitrogen atmosphere, 25 g (0.046 mol) of the compound of formula 104 prepared in Example 1-3, N- (biphenyl-4-yl) -9,9-dimethyl-9 H- 36 g of fluorene-2-amine, 0.10 g of palladium acetate (II), 1.9 g of tri- (t-butyl) phosphine (10% hexane solution), 11 g of sodium t-butoxide and 250 ml of toluene o-xylene were added thereto. . The reaction solution was refluxed for 12 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 41 g (yield 80%) of the title compound.

MS ( m / z , [M] ⁺ ): C 84 H 62 N 2: 1098.68 (1098.49).

Example 14

Fabrication of Organic Electroluminescent Device Using Formula 11

A transparent anode of indium tin oxide (ITO) having a 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. Subsequently, 2-TNATA of Chemical Formula 1 was deposited to have a thickness of 500 kPa, thereby forming a hole injection layer. Subsequently, the chemical formula 11 of the present invention was deposited to have a thickness of 300 kPa to form a hole transport layer. Subsequently, Alq ₃ of Formula 3 was deposited to a thickness of 500 kPa, thereby forming a light emitting layer. Finally, lithium fluoride (LiF) was deposited to have a thickness of 8 mW and aluminum was deposited to have a thickness of 1000 mW to form a cathode (see FIG. 7). The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

[Formula 1] [Formula 3]

Example 15

Fabrication of Organic Electroluminescent Device Using Chemical Formula 12

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 12 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 16

Fabrication of Organic Electroluminescent Device Using Formula 13

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 13 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 17

Fabrication of Organic Electroluminescent Device Using Formula 14

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 14 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 18

Fabrication of Organic Electroluminescent Device Using Formula 20

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 20 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 19

Fabrication of Organic Electroluminescent Device Using Chemical Formula 21

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 21 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 20

Fabrication of Organic Electroluminescent Device Using Chemical Formula 25

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 25 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Example 21

Fabrication of Organic Electroluminescent Device Using Chemical Formula 26

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14, except that Chemical Formula 26 was used instead of Chemical Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

[Example 22]

Fabrication of Organic Electroluminescent Device Using Chemical Formula 27

In Example 14, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14 except that Formula 27 was used instead of Formula 11 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

[Example 23]

Fabrication of Organic Electroluminescent Device Using Chemical Formula 17

A transparent anode of indium tin oxide (ITO) having a 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. Subsequently, the chemical formula 17 of the present invention was deposited to a thickness of 500 kPa to form a hole injection layer. Subsequently, NPB of Chemical Formula 2 was deposited to have a thickness of 300 GPa to form a hole transport layer. Subsequently, Alq ₃ of Chemical Formula 3 was deposited to have a thickness of 500 μs to form a light emitting layer. Finally, lithium fluoride (LiF) was deposited to have a thickness of 8 mW and aluminum was deposited to have a thickness of 1000 mW to form a cathode. The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

[Formula 2]

Example 24

Fabrication of Organic Electroluminescent Device Using Chemical Formula 23

In Example 23, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 23, except that Chemical Formula 23 was used instead of Chemical Formula 17 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

[Example 25]

Fabrication of Organic Electroluminescent Device Using Chemical Formula 24

In Example 23, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 23, except that Chemical Formula 24 was used instead of Chemical Formula 17 as the hole transport layer. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Comparative Example 1

Fabrication of organic electroluminescent device using 2-TNATA and NPB

In the present Comparative Example, the organic electroluminescent device was manufactured and evaluated in the same manner as in Example 14 except that the NPB of Formula 2, which is well known in the art, was used instead of Formula 11 as the hole transport layer in Example 14. Table 1 shows the emission characteristics measured at the applied voltage of 6V.

Table 1: Light emission characteristics of organic electroluminescent device

Example Compound of hole transport layer or hole injection layer Current density
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) Example 14 Formula 11 13.7 579 4.22 Example 15 Formula 12 15.2 636 4.18 Example 16 Formula 13 44.4 1609 3.62 Example 17 Formula 14 10.4 438 4.21 Example 18 Formula 20 27.4 1126 4.11 Example 19 Formula 21 12.4 472 3.81 Example 20 Formula 25 33.2 1319 3.97 Example 21 Formula 26 17.1 654 3.82 Example 22 Formula 27 22.0 850 3.86 Example 23 Formula 17 15.5 574 3.70 Example 24 Formula 23 14.2 599 4.21 Example 25 Formula 24 12.6 499 3.96 Comparative Example 1 Formula 1 (2-TNATA), Formula 2 (NPB) 12.6 425 3.38

As can be seen in Table 1, it can be seen that the organic electroluminescent device according to Examples 14 to 25 of the present invention generally has a higher current density, brightness and efficiency than Comparative Example 1.

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.

The organic light emitting composition and the organic electroluminescent device including the same according to the present invention are not only organic light emitting diodes but also organic field-effect transistors, organic thin film transistors, organic laser diodes, organic solar cells, organic light emitting electrochemical cells, and organic integrated circuits. Can also be used in the field.

1 is a UV / Vis for the triphenylene derivative of formula 12 according to the present invention. And fluorescence spectral graphs.

2 is a differential scanning calorimetry (DSC) curve graph of the triphenylene derivative of Formula 12 according to the present invention.

Figure 3 is a UV / Vis for the triphenylene derivative of formula 14 according to the present invention. And fluorescence spectral graphs.

4 is a differential scanning calorimeter curve graph of the triphenylene derivative of Formula 14 according to the present invention.

Figure 5 is a UV / Vis for the triphenylene derivative of formula 21 according to the present invention. And fluorescence spectral graphs.

Figure 6 is a UV / Vis for the triphenylene derivative of formula 25 according to the present invention. And fluorescence spectral graphs.

7 is a view showing a multilayer structure of an organic electroluminescent device manufactured using the triphenylene derivative according to the present invention.

Claims (3)

An organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device, comprises a triphenylene derivative represented by the following general formula (I). [Formula I]

(In formula (I), R1 and R2 are each hydrogen or an aryl group having 6 to 30 nuclear carbon atoms substituted or unsubstituted.) The organic electroluminescent composition according to claim 1, wherein Formula I is one of Formulas 11 to 23. [Formula 11] [Formula 12]

[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]

An organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition according to claim 1.

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