KR100679949B1 - Organic light emitting materials - Google Patents

Abstract

The present invention relates to a compound derivative used in an organic light emitting diode (OLED), an organic light emitting diode using the same, and a method for manufacturing the same. More specifically, a nonnaphthyl compound derivative of Formula 1 having a high glass transition temperature is prepared and organically produced. It is used as a hole transporting material of light emitting diodes to provide excellent thermal stability and device lifetime, and to provide an organic light emitting diode having excellent light emission brightness and light emission efficiency.

[Formula 1]

(In Formula 1, R1 or R2 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted anthryl group. May be the same or different from each other and directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.)

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

Description

Organic light emitting materials             

1 is a UV / Vis for the vinaphthyl derivative of formula 33 in accordance with the present invention. Spectral graph.

2 is a fluorescence spectrum graph of a vinapthyl derivative of Chemical Formula 33 according to the present invention.

Figure 3 is a differential scanning calorimetry (DSC) curve graph for the vinapthyl derivative of formula 33 in accordance with the present invention.

4 is a thermogravimetric analyzer (TGA) curve graph of the vinapthyl derivative of Formula 33 according to the present invention.

5 is a view showing a multi-layered structure of an organic light emitting diode manufactured using the vinaphthyl derivative according to the present invention.

FIG. 6 is another diagram illustrating a multilayer structure of an organic light emitting diode manufactured using the vinaphthyl derivative according to the present invention.

The present invention relates to a compound derivative used in an organic light emitting diode (OLED), an organic light emitting diode using the same, and a method for manufacturing the same. More specifically, a compound of Formula 1, which is a vinapthyl derivative having a high glass transition temperature, is prepared. It is to provide an organic light emitting diode having excellent thermal stability and lifespan, and excellent light emitting brightness and light emitting efficiency by using as a hole transport material of an organic light emitting diode. 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 a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted anthryl group. May be the same or different from each other and directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.)

Organic light-emitting diodes (OLEDs), which have many advantages such as low voltage driving, self-luminous, light weight, wide viewing angle, and fast response time, are one of the next generation flat panel displays to replace LCDs, and are currently being actively researched. to be.

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. However, 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, particularly the hole transport material, must have thermal and electrical stability. Because of the heat generated from the device when the voltage is applied, the low thermal stability molecules have low crystal stability, resulting in rearrangement, and eventually localization of crystallization causes an electric field to concentrate on this area. This is because it is considered 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]

However, since CuPC is a metal complex, it is widely used because it has excellent adhesion to ITO substrate and is the most stable, but it is difficult to realize total color due to absorption in the visible region, and m-MTDATA or 2-TNATA have a glass transition temperature. Is not only low as 78 ℃ 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 binaphthyl derivative represented by the following Chemical Formula 1, which is useful as a hole transporting material in an organic light emitting diode, and derivatives having the basic structure of the Chemical Formula 1 have a high glass transition temperature (145 ° C or higher). Fabrication of organic light emitting diodes using hole transport materials can increase luminous efficiency and increase device life.

[Formula 1]

(In Formula 1, R1 or R2 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted anthryl group. May be the same or different from each other and directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.)

Another feature of the present invention is that the binaphthyl derivative represented by Chemical Formula 1 is represented by the general formula RR'NH (wherein R and R 'represents a hydrocarbon residue) to the tetrahalo compound represented by Chemical Formula 11 below. Vinaphthyl derivatives prepared by reacting secondary amines.

[Formula 11]

(In Formula 11, X ₂ is a halogen atom, preferably represents a chlorine atom or bromine atom.)

In addition, the binaphthyl derivative represented by Formula 1 may be represented by Formulas 33 to 49, wherein R1 or R2 is specifically specified, and general formula RR'NH (where R and R 'are hydrocarbon residues). It is another feature of the present invention that the secondary amine represented by the present invention relates to the binaphthyl derivative represented by the formulas (16) to (32). Specific formulas are shown below in detail in the relevant parts.

According to another preferred embodiment of the present invention, in using the non-naphthyl derivative as the hole transport material, an organic light emitting diode may be manufactured using the hole injection material, the hole transport material, or the light emitting layer material.

Another preferred embodiment of the present invention is characterized in that the tetrahalo compound represented by Chemical Formula 11 is reacted with a secondary amine represented by the general formula RR'NH (wherein R and R 'represent a hydrocarbon residue). It relates to a method for producing a binaphthyl derivative represented by the formula (1). In addition, the reaction of the tetrahalo compound with a secondary amine represented by the general formula RR'NH (wherein R and R 'represent hydrocarbon residues) includes a catalyst and a reaction base containing a palladium compound and a phosphine compound. And it may be made in the presence of a reaction solvent, in the case of using a copper catalyst may be made in the presence of a reaction base or a reaction base and a reaction solvent, as a specific example, the palladium compound is palladium acetate or tris (dibenzylideneacetone) Palladium (0), or the phosphine compound is tri- o -tolylphosphine, 2,2'-bis (diphenylphosphino) -1,1'-binafthyl, tri-n-butylphosphine or tri- t-butylphosphine or the reaction base is a metal alkoxide such as sodium t-butoxide or potassium t-butoxide, or the reaction solvent is benzene, toluene, xylene, N, N -dimethylformamide or N, N- Dime And it characterized in that the sulfoxide is capable of producing a binaphthyl derivative.

As described above, the present invention is to prepare a vinaphthyl derivative of Formula 1, specifically, a vinaphthyl derivative represented by Formula 33 to Formula 49, which is used as a hole transporting material of an organic light emitting diode, which is represented by Formula 11 It is a main technical feature of the present invention that the tetrahalo compound is formed by amination reaction with secondary amines represented by the formulas (16) to (32). And the tetrahalo compound represented by Formula 11 was prepared from the compound of Formula 10, the compound of Formula 10 was prepared from the material of Formula 9, the compound of Formula 9 was prepared by reacting Formula 7 and Formula 8 .

Hereinafter, the process of preparing the vinaphthyl derivative according to the present invention will be described in order over time. First, the present inventors synthesized vinaphthyl of the following Chemical Formula 9 through Suzuki coupling using 1-naphthalene boronic acid of the following Chemical Formula 7 and 1-bromonaphthalene of the following Chemical Formula 8.

[Formula 7]

[Formula 8]

[Formula 9]

Synthesis was carried out by the method used for conventional Suzuki coupling. The reaction solvent used is not particularly limited, and general Suzuki coupling solvents such as aromatic solvents such as benzene, toluene or xylene, alcohols such as ethanol or isopropyl alcohol, and water or N, N -dimethylform A solvent such as amide or tetrahydrofuran may be used. The palladium catalyst used in the reaction is tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) or [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) chloride (Pd (dppf) Cl ₂ ) is suitable, and the reaction base is a metal carbonate such as sodium carbonate or potassium carbonate, metal alkoxide such as sodium ethoxide, sodium t-butoxide, potassium t-butoxide, diethylamine or tri What is chosen from amine bases, such as ethylamine, can be used individually or in mixture. In order to facilitate the reaction, a phase transfer catalyst such as tetrabutylammonium bromide may be used together.

4,4'-dihalo-1,1'-binaftil of the following Chemical Formula 10 was synthesized by reacting the 1,1'-binafyl and the halogenating reagent of Formula 9 prepared above. The halogenating reagent used in the reaction is preferably bromine (Br ₂ ), iodine (I ₂ ), potassium iodide (KI) or potassium iodate (KIO ₃ ). In the bromination reaction, chloroform or dichloromethane is suitable, and in the iodide reaction, sulfuric acid or nitric acid may be added to acetic acid or acetic acid, or both sulfuric acid and nitric acid may be used.

[Formula 10]

(In Formula 10, X ₁ is a halogen atom, preferably a bromine atom (Formula 51) or an iodine atom (Formula 52).)

There are three methods for synthesizing the tetrahalo compound of Formula 11 from 4,4'-dihalo-1,1'-binafyl of Formula 10 prepared above.

The first method is a method of synthesizing the compound of Formula 10 by reacting boronic acid of Formula 12. When boron acid used in the reaction is a starting material, the halogen atom (X ₁ ) in the formula (10) is bromine; When 5-dichlorobenzeneboronic acid is used and the halogen atom (X ₁ ) is iodine, 3,5-dibromobenzeneboronic acid is used. Other reaction conditions, that is, the reaction solvent, the reaction catalyst and the reaction base are the same as in the Suzuki coupling to produce the formula (9) in the formula (7).

[Formula 11]

(In Formula 11, X ₂ is a halogen atom, preferably a chlorine atom (Chemical Formula 53) or bromine atom (Chemical Formula 54).)

[Formula 12]

(In Formula 12, X ₂ is a halogen atom, preferably a chlorine atom or bromine atom.)

The second method of preparing Formula 11 from Formula 10 is to synthesize a boronic acid compound of Formula 13 using a borate compound and then react with 1,3,5-tribromobenzene of Formula 14 To prepare the formula (11). The borate compound used for the reaction is a common borate compound, preferably trimethyl borate or triisopropyl borate. The base used for the reaction mainly uses butyl lithium as a strong base. The reaction solvent is not reactive with the strong base used, and ether or tetrahydrofuran is used, and a normal acid, that is, sulfuric acid or hydrochloric acid, is used to complete the reaction. The compound of Formula 11 may be prepared by using Suzuki coupling of diboronic acid of Formula 13 and 1,3,5-tribromobenzene of Formula 14 obtained above. The preparation method is the same as the method for preparing the compound of Formula 11 from the compound of Formula 10.

[Formula 13]

[Formula 14]

A third method of preparing the compound of Formula 11 from the compound of Formula 10 is to use a Grignard compound. Synthesis of the Grignard compound of Formula 15 using magnesium in Formula 10, and through the Grignard reaction with the compound of Formula 14 to prepare a compound of Formula 11. The reaction solvent used for the production of the Grignard compound and the Grignard reaction is not particularly limited and may be any solvent which is not reactive and soluble in the Grignard compound. Preferably, ethers such as diethyl ether or tetrahydrofuran or aromatic solvents such as benzene or toluene are used. As the catalyst used in the reaction, a palladium catalyst such as dichlorobis (triphenylphosphine) palladium (II) may be used, and a phosphine catalyst such as tri- o -tolylphosphine may be used together if necessary. The reaction base uses diisobutylaluminum hydride, which is a relatively strong base.

[Formula 15]

(In Formula 15, X ₁ is a halogen atom, preferably a bromine atom or an iodine atom.)

The compound of Formula 11 is reacted with various amines to finally prepare a hole transport material useful for a high performance organic light emitting diode. There are two main methods for the conditions used for the amination reaction.

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 potassium carbonate or sodium carbonate is most suitable. N, N -dimethylsulfoxide, nitrobenzene or decalin are used, either without reaction solvent or with a high boiling point. Sometimes crown ethers or poly (ethylene glycol) are used to make the reaction smoother.

The second method is a method using a palladium catalyst. The amination reaction is carried out 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 mainly palladium acetate or tris (Dibenzylideneacetone) palladium (0) is used, and the phosphine catalyst is not particularly limited, and tri- o -tolylphosphine, 2,2'-bis (diphenylphosphino) -1,1'-binaf Tyl, tri-n-butylphosphine or tri-t-butylphosphine 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 the secondary amine used in the amination reaction include a compound represented by any one of the following Chemical Formulas 16 to 32.

[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] [Formula 31]

[Formula 32]

Specific examples of the hole transport material which enables the organic light emitting diode having high luminous efficiency and long lifetime through the amination reaction may include a compound represented by one of the following Chemical Formulas 33 to 49. However, the present invention is not limited to these.

[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]

[Formula 49]

Vinaphthyl derivative of the formula (1) of the present invention can be prepared in the same manner as described above, using this as a hole transporting material of the organic light emitting diode can obtain a high luminous efficiency and excellent durability because the glass transition temperature is high A device can be manufactured. The hole transport material herein refers to a material used for the hole injection layer, the hole transport layer, and sometimes the light emitting layer. In addition, 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, so that the compound of Formula 1 may be effectively used to manufacture a display device of all natural colors, and thus has high durability and high performance. It is possible to manufacture a full color display device.

[Formula 1]

(In Formula 1, R1 or R2 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted anthryl group. R1 and R2 represent each other. It may be the same or different and may be directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.)

Vinaphthyl derivatives represented by Formula 1 of the present invention synthesized as described above were purified using recrystallization and sublimation in view of the characteristics of organic light emitting diodes requiring high purity. Detailed description of synthesis can be found in the synthesis examples. The physical and photochemical properties of Chemical Formula 33 and Chemical Formula 45 prepared through the purification process are shown in Table 1 below.

TABLE 1

(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 compounds of Formula 33 and Compound 45 were measured for UV maximum absorption wavelengths (λ _max ), respectively, and were 324 nm and 293 nm, respectively. Shown in As shown in FIG. 1, the maximum UV absorption wavelength (λ _max ) of the compound of Formula 33 is 324 nm.

Using the maximum absorption wavelength as the excitation wavelength, photoluminescence (PL) spectra were measured for the compounds of Formula 33 and the compounds of Formula 45, respectively, and the maximum peaks were measured at 436 nm and 407 nm. 2 shows the measurement results for the compound of Chemical Formula 33, which can be seen that it emits blue light. Therefore, the compound of Formula 33 and the compound of Formula 45 are suitable hole transport materials to achieve the full color.

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 33 and Formula 45 was 297 ° C. and 289 ° C., respectively, and the glass transition temperatures were observed at 148 ° C. and 208 ° C. or higher. Therefore, 2-TNATA [4,4 ', 4' '-tris (N- (niphthylene-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 a device, it is possible to manufacture a device with a long lifespan. Measurement results of the compound of Formula 33 are shown in FIG. 3.

As a result of thermogravimetric analysis (TGA), a weight loss of 1% of the compound of Formula 33 and Formula 45 was observed at 478 ° C and 495 ° C, respectively. Thermal stability is possible even at high temperatures, so there is no risk of decomposition during vacuum deposition during device fabrication. Measurement results of the compound of Formula 33 are shown in FIG. 4.

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 examples, the results of measuring the electroluminescent properties are shown in Table 2 and Table 3 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 Chemical Formula 50, as a light emitting layer material. Table 3 shows the results of Example 6 and Comparative Example 2 of the organic light emitting diode using the blue light emitting material as the material of the light emitting layer.

[Formula 50]

TABLE 2

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 33 and the compound of Formula 45 as a hole transport material, specifically, a hole injection layer at an applied voltage of 10V. It was produced to measure the light emission characteristics. The compound of Formula 33 is produced in a thickness of 400 kPa (Example 1), 500 kPa (Example 2), 600 kPa (Example 3), 800 kPa (Example 4), respectively, and the thickness of the compound of Formula 45 and the comparative material 2 -TNATA was fabricated at 600 Å to examine the luminescence properties (Example 5, Comparative Example 1). When the compound of Chemical Formula 33 and the compound of Chemical Formula 45 were used as the hole transporting material, the light emission characteristics were excellent in all aspects of current density, brightness, highest brightness, and luminous efficiency than 2-TNATA, which is a comparative material, regardless of the deposition thickness. It was. The compound of Formula 45 exhibited better emission characteristics than the compound of Formula 33 at the same 600 μs thickness, and when the compound of Formula 33 was deposited at 500 μs by the deposition thickness (Example 2), the best emission characteristics were obtained. Indicated.

TABLE 3

Table 3 shows the emission of organic light emitting diodes using the light emitting layer as a blue light emitting material and using the compound of Formula 33 as a hole transport material, specifically, a hole injection layer at the same 1000 Cd / m ² emission luminance. The properties were measured. The compound of Chemical Formula 33 showed a low applied voltage and high luminous efficiency compared to 2-TNATA as a comparative material at 1000 Cd / m ² emission luminance. In addition, the quantum efficiency measurement result is also about 30% higher than 2-TNATA. In the case of 2-TNATA, the color coordinate shift occurs a lot in the blue light emission. Since the y coordinate is increased among the color coordinates, it is difficult to implement pure blue color because there is a lot of movement toward green. On the other hand, in the compound of Chemical Formula 33 of the present invention, since almost no color coordinate shift occurs, pure blue may be effectively implemented, and thus, may be effectively used to fabricate a display device having a total color.

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 1,1'-Vinaphthyl (Formula 9)

Into a 10000-ml, four-necked round bottom flask, 110.0 g (0.53 mol) of 1-bromonaphthalene is added and diluted with 4400 ml of toluene and 1700 ml of ethanol. 100.5 g (0.58 mol) of 1-naphthalene boronic acid and 13.7 g (0.043 mol) of tetrabutylammonium bromide were added to the diluent, and an aqueous solution in which 293.7 g (2.12 mol) of potassium carbonate was completely dissolved in 2600 ml of distilled water was added thereto. Tetrakis (triphenylphosphine) palladium (0) 18.42 g (0.016 mol) was added to the mixed solution, and the reaction solution was refluxed for 1 day while blocking light. After cooling the reaction solution to room temperature, the organic layer was separated, water was removed, and then concentrated. The obtained solid was suspended and stirred in diethyl ether, filtered and washed with diethyl ether. The washed solid compound was vacuum dried to obtain 123 g (yield 91%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.96 (dd, J = 8.2, 4.6 Hz, 4H), 7.60 (t, J = 7.1 Hz, 2H), 7.51-7.47 (m, 4H), 7.40 (d, J = 8.5 Hz, 2H), 7.29 (t, J = 7.9 Hz, 2H).

The synthetic route of Formula 9 is shown in Scheme 1 below.

Scheme 1

Synthesis Example 2

Preparation of 4,4'-dibromo-1,1'-vinaphthyl (Formula 51: One of Formula 10)

In this synthesis example, 4,4'-dibromo-1,1'-binafyl represented by Chemical Formula 51 was prepared, which is a case where halogen atom X ₁ in Chemical Formula 10 is a bromine atom.

A stirrer and a reflux apparatus were installed in a 2000-ml, four-necked round bottom flask, and 107 g (0.421 mol) of 1,1'-binafthyl prepared above was dissolved in 1000 ml of dichloromethane. 43.1 ml of bromine was slowly added to this dilution and stirred at room temperature for 1 hour. Caustic soda solution is added to the reaction solution to complete the reaction, and the organic layer is separated and concentrated. The obtained solid was collected and dried in vacuo to yield 161.4 g (yield 93%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 8.38 (d, J = 8.6 Hz, 2H), 7.91 (d, J = 7.5 Hz, 2H), 7.63-7.59 (m, 2H), 7.36 (d, J = 3.8 Hz , 4H), 7.33 (d, J = 7.5 Hz, 2H).

The synthetic route of Formula 51 is shown in Scheme 2 below.

Scheme 2

Synthesis Example 3

Preparation of 4,4'-Diiodo-1,1'-Vinaphthyl (Formula 52: One of Formula 10)

In this synthesis example, 4,4'-dioodo-1,1'-binafthyl represented by Chemical Formula 52 was prepared, which is a case where halogen atom X ₁ in Chemical Formula 10 is an iodine atom.

A 250-ml, three-necked round bottom flask was charged with 2g (7.86mmol) of 1,1'-binafthyl, 78ml of acetic acid and 2g (7.88mmol) of iodine. 4 ml of concentrated sulfuric acid and 1.57 ml of 69% nitric acid were added to the reaction solution in this order. The reaction was refluxed for 4 hours and left at room temperature for 2 hours. Extracted using aqueous sodium bicarbonate solution and dichloromethane, the organic layer was separated, dried and concentrated. The obtained solid was collected and dried in vacuo to yield 3.2 g (yield 81%) of a yellow target compound.

¹ H NMR (CDCl ₃ ): δ 8.65 (d, J = 8.8 Hz, 2H), 8.33 (d, J = 7.7 Hz, 2H), 7.78 to 7.74 (m, 2H), 7.57 (d, J = 7.7 Hz , 2H), 7.50-7.47 (m, 2H), 7.39 (d, J = 8.5 Hz, 2H).

The synthetic route of Formula 52 is shown in Scheme 3 below.

Scheme 3

Synthesis Example 4

Preparation of 1,1'-binafyl-4,4'-diboronic acid (Formula 13)

4,4'-Dibromo-1,1'-binaftil 52g prepared in the same manner as in Synthesis Example 2 with a stirrer in a 20000-ml, 5-necked round bottom flask and completely dried. (0.13 mol) was added thereto and dissolved in 260 ml of dried tetrahydrofuran. The above solution was cooled to -50 ° C and slowly added 126 ml of butyllithium (2.5 N -hexane solution) at the same temperature, followed by stirring for 30 minutes. A solution obtained by diluting 116 ml of triisopropyl borate in 260 ml of tetrahydrofuran was slowly added to the reaction solution while maintaining the temperature below -50 ° C. The temperature of the reaction solution was slowly raised to room temperature, and 520 ml of 10 N hydrochloric acid aqueous solution was added thereto, followed by stirring for 1 hour. Water and dichloromethane were added to the reaction mixture to extract the target compound, followed by removal of water and concentration. The obtained solid was suspended and stirred in hexane, filtered and dried in vacuo to give 26.3 g (yield 61%) of the title compound.

¹ H NMR (DMSO-d6): δ 8.48-7.46 (complex, 6H), 7.85 (d, J = 6.9 Hz, 2H), 7.50 (t, J = 6.5 Hz, 2H), 7.43 (d, J = 6.9 Hz, 2H), 7.30 (t, J = 7.5 Hz, 2H), 7.20 (d, J = 8.4 Hz, 2H).

The synthetic route of Formula 13 is shown in Scheme 4 below.

Scheme 4

Synthesis Example 5

Preparation of 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binafthyl (Formula 53: one of Formula 11)

In this synthesis example, 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binafthyl represented by Chemical Formula 53 was prepared, and when the halogen atom X ₂ in Chemical Formula 11 was a chlorine atom to be.

Into a 20000-ml, 5-neck round bottom flask, 4,4'-dibromo-1,1'-binafthyl 135g (0.33mol) prepared in the same manner as in Synthesis Example 2 was added, and 5400ml of toluene and 2100ml of ethanol were added. Suspended. 137.5 g (0.72 mol) of 3,5-dichlorobenzeneboronic acid was added to the suspension, and an aqueous solution in which 362 g (2.62 mol) of potassium carbonate was completely dissolved in 3200 ml of distilled water was added thereto. 22.71 g (0.02 mmol) of tetrakis (triphenylphosphine) palladium (0) was added to the above suspension, and the reaction solution was refluxed for 1 day while blocking the light. After cooling the reaction solution to room temperature, the organic layer was separated, water was removed, and then concentrated. The obtained solid was suspended and stirred in acetone, filtered and washed with acetone. The washed solid compound was vacuum dried to obtain 151 g (yield 85%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.93 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 7.1 Hz, 2H), 7.55-7.48 (m, 12H), 7.36 (t, J = 7.1 Hz , 2H).

The synthetic route of Formula 53 is shown in Scheme 5 below.

Scheme 5

Synthesis Example 6

Preparation of 4,4'-bis- (3,5-dibromophenyl) -1,1'-binafthyl (a kind of Formula 54: Formula 11)

In this synthesis example, 4,4'-bis- (3,5-dibromophenyl) -1,1'-binapthyl represented by Chemical Formula 54 was prepared, and the halogen atom X ₂ in the formula 11 was a bromine atom. If

31.5 g (0.092 mol) of 1,1'-binafthyl-4,4'-diboronic acid prepared in the same manner as in Synthesis Example 4 was added to a 5000-ml, four-necked round bottom flask, and 1260 ml of toluene and 500 ml of ethanol. Dissolved. 87 g (0.276 mol) of 1,3,5-tribromobenzene was added to this solution, and an aqueous solution in which 102 g (0.736 mol) of potassium carbonate was completely dissolved in 760 ml of distilled water was added thereto. Tetrakis (triphenylphosphine) palladium (0) 7.45 g (6.44 mmol) was added to the above suspension, and the reaction solution was refluxed for 1 day while blocking light. After cooling the reaction solution to room temperature, the organic layer was separated, water was removed, and then concentrated. The obtained solid was suspended and stirred in ethyl acetate, filtered and dried in vacuo to give 55.9 g (yield 84%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.91 (d, J = 8.2 Hz, 2H), 7.79 (t, J = 1.7 Hz, 2H), 7.71 (d, J = 1.6 Hz, 4H), 7.65 (d, J = 7.2 Hz, 2H), 7.52-7.48 (m, 6H), 7.35 (t, J = 7.1 Hz, 2H).

The synthetic route of Formula 54 is shown in Scheme 6 below.

Scheme 6

Synthesis Example 7

Other Preparations of 4,4'-bis- (3,5-dibromophenyl) -1,1'-binafthyl (a kind of Formula 54: Formula 11)

In this synthesis example, 4,4'-bis- (3,5-dibromophenyl) -1,1'-binapthyl represented by Chemical Formula 54 was prepared according to a method different from that of Synthesis Example 6, This is the case when the halogen atom X ₂ in the formula (11) is a bromine atom.

500-ml, three-necked round bottom flask was dried well, and 3.72 g (0.153 mol) of magnesium, a small amount of iodide, and 120 ml of tetrahydrofuran were added under a nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour, diluted in 220 ml of tetrahydrofuran, and 30 g (0.0728 mol) of 4,4'-dibromo-1,1'-binafthyl (Formula 51) prepared above was added to the mixture. Slowly added. After the addition was completed, the reaction solution was refluxed for 1 hour.

57.3 g (0.182 mol) of 1,3,5-tribromobenzene, dichlorobis (triphenylphosphine) palladium 0.51 g (0.73 mmol), tri-o-tolyl in a dried 1000-ml, four-necked round bottom flask 0.11 g (0.36 mmol) of phosphine, 7.28 ml of a 1 M -toluene solution of diisobutylaluminum hydride and 300 ml of tetrahydrofuran were charged under a nitrogen atmosphere. The Grignard reagent prepared above was slowly added to the mixed solution and refluxed for 1 day. After the reaction solution was cooled to 5 ° C, the reaction was terminated with dilute hydrochloric acid aqueous solution. Dichloromethane was used to extract the target compound, remove moisture, and concentrate. The obtained solid was suspended and stirred in ethyl acetate, filtered and dried in vacuo to give 45.2 g (yield 86%) of the title compound. The resulting solid was filtered off and washed with water and methanol. The obtained solid compound was vacuum dried to obtain 47.2 g (yield 86%) of the title compound.

The synthetic route of Formula 54 is shown in Scheme 7 below.

Scheme 7

Synthesis Example 8

Preparation of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

This synthesis example is a tetrahalo compound prepared in the formula (11), that is, formula 53 or formula 54, induces an amination reaction with secondary amines, vinapyl derivative represented by the formula (1) according to the present invention (Formula 1 Example of preparing 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl represented by Formula 33 as one of the preferred embodiments of It is about. As a condition of the amination reaction in this synthesis example, the Uulman reaction using a copper catalyst was used, and preferably copper powder is used.

4,4'-bis- (3,5-dibromophenyl) -1,1'-binafthyl (Formula 54) prepared in the same manner as in Synthesis Example 6 in a 500-ml, three-neck round bottom flask. To 31.5 g (0.0436 mol), 32.5 g (0.192 mol) of diphenylamine, 36.17 g (0.262 mol) of potassium potassium carbonate and 0.28 g (4.36 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 then dried in vacuo to give 41.3 g (yield 88%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.97 (d, J = 9.0 Hz, 2H), 7.45 (d, J = 7.2 Hz, 2H), 7.38 (dd, J = 7.2, 1.3 Hz, 6H), 7.25-7.72 (m, 18H), 7.18-7.16 (m, 16H), 6.98-6.14 (m, 10H), 6.88 (d, J = 2.0 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C80H58N4: 1075.2334 (1075.47)

EA: C, 89.1649%; H, 5.3952%; N, 5.1268% (C, 89.35%; H, 5.44%; N, 5.21%)

UV (λ _max ): 324nm

PL: 436nm

Melting Point (mp): 297 ℃

Glass transition temperature (measured by Tg, DSC): 148 ℃

1% weight loss temperature (measured by TGA): 478 ℃

The synthetic route of Formula 33 is shown in Scheme 8 below.

Scheme 8

Synthesis Example 9

Other Preparations of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

Synthesis Example 9 is to prepare a vinaphthyl derivative represented by the formula (33) in the same conditions as in Synthesis Example 8 using a copper catalyst, and unlike the Synthesis Example 8 includes a poly (ethylene glycol) as a reaction additive and react Decalin is further included as a solvent.

31.5 g (0.0436) of 4,4'-bis- (3,5-dibromophenyl) -1,1'-binaftil prepared in the same manner as in Synthesis Example 6 in a 500-ml, three-neck round bottom flask mol), 32.5 g (0.192 mol) of diphenylamine, 2.68 g of poly (ethylene glycol) 6000, 36.17 g (0.262 mol) of potassium carbonate, 0.28 g (4.36 mmol) of copper powder, and 158 ml of decalin are added. The reaction solution was heated to reflux with stirring. After refluxing for 36 hours, the reaction solution was cooled to 60 ° C. while adding an appropriate amount of decalin to prevent the reaction solution from solidifying. 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 46.9 g (yield 100%) of the title compound.

Synthesis Example 10

Another Preparation of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

Synthesis Example 10 is to prepare a vinaphthyl derivative represented by the formula (33) in the same manner as in Synthesis Example 8, but, unlike Synthesis Example 8, using a palladium catalyst and a phosphine catalyst under the conditions of the amination reaction, preferably Palladium acetate and tri-t-butylphosphine. It was prepared in the presence of sodium t-butoxide as the base and toluene as the reaction solvent.

4,4'-bis- (3,5-dibromophenyl) -1,1'-binaftil prepared in the same manner as in Synthesis Example 6 by mounting a stirrer in a 2000-ml, four-necked round bottom flask 95 g (0.132 mol), 98 g (0.579 mol) diphenylamine, 0.295 g (1.32 mmol) palladium acetate, 10.64 g tri-t-butylphosphine (10% hexane solution), 61.2 g sodium t-butoxide (0.637 mol) ) And 760 ml of toluene was added thereto. The reaction solution was refluxed for 3.5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 138.6 g (yield 98%) of the title compound.

Synthesis Example 11

Another Preparation of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

Synthesis Example 11 was prepared in the same manner as in Synthesis Example 10, except that tris (dibenzylideneacetone) palladium (0) was used instead of the palladium acetate used in Synthesis Example 10 as the reaction catalyst, to obtain 133.0 g of the target compound (yield). 94%).

Synthesis Example 12

Another Preparation of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

Synthesis Example 12 was prepared by the same method as Synthesis Example 10, except that tri ( o -tolyl) phosphine was used instead of the tri-t-butylphosphine used in Synthesis Example 10 as the reaction catalyst, and the target compound was 128.7 g. (Yield 91%) was obtained.

Synthesis Example 13

Preparation of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33)

Synthesis Example 13 is to prepare a vinaphthyl derivative represented by the formula (33) as in Synthesis Example 10, but 4,4'-bis- (3,5-dibromophenyl) -1,1'-binaf 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binafthyl (Formula 53) is used instead of butyl (Formula 54).

A 500-ml, 4-necked round bottom flask was equipped with a stirrer and 35 g of 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binaftil prepared in the same manner as in Synthesis Example 5. 0.0643 mol), 47.9 g (0.283 mol) diphenylamine, 0.144 g (0.64 mmol) palladium acetate, 5.20 g tri-t-butylphosphine (10% hexane solution), 29.9 g (0.311 mol) sodium t-butoxide And 280 ml of o-xylene was added. The reaction solution was refluxed for 4.0 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to afford 66.4 g of the target compound (yield 96%).

The synthetic route of Formula 33 is shown in Scheme 9 below.

Scheme 9

Synthesis Example 14

Preparation of 4,4'-bis- (3,5-di- (dicarbazolyl) -phenyl) -1,1'-binafthyl (Formula 45)

This synthesis example is one of the preferred embodiments of the vinaphthyl derivative represented by the formula (1) according to the present invention (Formula 1) 4,4'-bis- (3,5-bis- (dicarba) represented by the formula (45) Zolyl) -phenyl) -1,1'-binafthyl. Here, 4,4'-bis- (3,5-dibromophenyl) -1,1'-binafthyl (Formula 54) was used as a tetrahalo compound as shown in Formula 11, and as a secondary amine, It is characterized by using a sol.

4,4'-bis- (3,5-dibromophenyl) -1,1'-binaftil prepared in the same manner as in Synthesis Example 6 with a stirrer in a 1000-ml, four-necked round bottom flask. 52 g (0.096 mol), carbazole 53 g (0.317 mol), palladium acetate 0.162 g (0.72 mmol), tri-t-butylphosphine (10% hexane solution) 5.83 g, sodium t-butoxide 433.5 g (0.349 mol) and 410 ml of o -xylene were added. 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 under vacuum to obtain 76.9 g (yield 100%) of the title compound.

^{1 H NMR (DMSO-d6)} : δ 8.32 (d, J = 8.6Hz, 2H), 8.29 (d, J = 7.7Hz, 8H), 8.04 (t, J = 1.8Hz, 2H), 7.99 (d, J = 1.8 Hz, 4H), 7.97 (d, J = 7.3 Hz, 2H), 7.79 (d, J = 8.3 Hz, 8H), 7.72-7.62 (m, 4H), 7.55-7.52 (m, 8H), 7.43 (d, J = 3.7 Hz, 4H), 7.34 (t, J = 7.5 Hz, 8H).

MALDI-TOF mass (M + H ⁺ ): C80H50N4: 1067.4698 (1067.4035)

EA: C, 89.9642%; H, 4.5951%; N, 5.1977% (C, 90.03%; H, 4.72%; N, 5.25%).

UV (λ _max ): 293nm

PL: 407nm

Melting Point (mp): 289 ℃

Glass transition temperature (measured by Tg, DSC): 208 ℃

1% weight loss temperature (measured by TGA): 495 ℃

The synthetic route of Formula 45 is shown in Scheme 10 below.

Scheme 10

Synthesis Example 15

Other Preparations of 4,4'-bis- (3,5-di- (dicarbazolyl) -phenyl) -1,1'-binafthyl (Formula 45)

Synthesis Example 15 prepared 4,4'-bis- (3,5-bis- (dicarbazolyl) -phenyl) -1,1'-binaftil represented by Chemical Formula 45 as in Synthesis Example 14. In this case, 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binafthyl (Formula 53) was used as the tetrahalo compound represented by Chemical Formula 11, and as the secondary amine, It is characterized by using carbazole.

52 g of 4,4'-bis- (3,5-dichlorophenyl) -1,1'-binaftil prepared in the same manner as in Synthesis Example 5 with a stirrer in a 1000-ml, four-necked round bottom flask; 0.096 mol), carbazole 70.3 g (0.420 mol), tris (dibenzylideneacetone) palladium 0.659 g (0.72 mmol), tri-t-butylphosphine (10% hexane solution) 7.73 g, sodium t-butoxide 44.44 g (0.462 mol) and o -xylene 410 ml were added. The reaction solution was refluxed for 20 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 76.1 g (yield 99%) of the target compound.

The synthetic route of Formula 45 is shown in Scheme 11 below.

Scheme 11

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. As a material of the light emitting layer, Alq ₃ [Tris (8-hydroxyquinolinol)] of Formula 50 is used. The light emitting layer was formed by evaporation to a thickness of 500 kPa. As can be seen in Table 2, Examples 1 to 4 were used as a hole-transfer material using a non-naphthyl derivative according to formula 33, each embodiment is characterized in that produced by varying the thickness of the hole injection layer It is done. In Example 5, a vinapthyl derivative according to Chemical Formula 45 was used as a hole transporting material, and Comparative Example 1 prepared a light emitting layer having the same thickness as that of Example 3 and Comparative Example 5 using 2-TNATA. .

Example 1

Fabrication of an organic light emitting diode having a thickness of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33) having a thickness of 400 Hz

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. Subsequently, 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binaftil of the chemical formula 33 of the present invention was deposited to have a thickness of 400 GPa, and the hole injection layer Was formed. 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-hydroxyquinolinol)] of Formula 50 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 14V 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. The results are shown in Table 2 below.

[Formula 6]

[Formula 50]

Example 2

Fabrication of an organic light emitting diode having a thickness of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33) of 500 Hz

In Example 1, 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl in Chemical Formula 33 was 500 kPa instead of 400 kPa. An organic light emitting diode was manufactured and evaluated in the same manner as in Example 1, except that it was increased.

Example 3

Fabrication of an organic light emitting diode having a thickness of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33) of 600 Hz

In Example 3, 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl in Chemical Formula 33 was 600 kPa instead of 400 kPa. An organic light emitting diode was manufactured and evaluated in the same manner as in Example 1, except that it was increased.

Example 4

Fabrication of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33) with an organic light emitting diode having a thickness of 800 Hz

In Example 3, 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafryl of the formula 33 in Example 1 was 800Å instead of 400Å. An organic light emitting diode was manufactured and evaluated in the same manner as in Example 1, except that it was increased.

Example 5

Fabrication of an organic light emitting diode having a thickness of 4,4'-bis- (3,5-bis- (dicarbazolyl) -phenyl) -1,1'-binafthyl (Formula 45) of 600 Hz

In Example 5, the non-naphthyl derivative according to Chemical Formula 45 was used as the hole transporting material, and the hole injection layer was formed by depositing a thickness of 600 kPa.

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. Subsequently, the hole injection layer was formed by depositing 4,4'-bis- (3,5-di- (dicarbazolyl) -phenyl) -1,1'-binaftil of Formula 45 to a thickness of 600 mm 3. . 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-hydroxyquinolinol)] of Formula 50 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 14V 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.

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 fabricated using the conventionally known 2-TNATA with the same thickness (600 Pa) as in Example 3 and Example 5.

In place of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl in Chemical Formula 33, 2-TNATA [4,4 ', An organic light-emitting diode was manufactured and evaluated in the same manner as in Example 3, except that 4 ″ -tris ( N- (2-naphthyl) -N -phenylamino) -triphenylamine] was used as the hole injection layer.

[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

Meanwhile, in Examples 1 to 5 and Comparative Example 1, Alq ₃ [tris (8-hydroxyquinolinol)] of Chemical Formula 50 was used as the material of the light emitting layer. Hereinafter, a blue light emitting material was used as the material of the light emitting layer. One form of a preferred embodiment of an organic light emitting diode manufactured using is described. As can be seen in Table 3 above, Example 6 was used as a hole transporting material, a non-naphthyl derivative according to formula 33, the thickness of the hole injection layer is characterized in that the production to 600Å. In addition, Comparative Example 2 replaces conventionally well-known 2-TNATA with 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33). An organic light emitting diode was manufactured in the same manner as in Example 6, except that there was used as the hole injection layer.

Example 6

4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl (Formula 33) having a thickness of 600 하여 using a blue light emitting material as a light emitting layer material Diode fabrication

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. Subsequently, the hole injection layer was formed by depositing 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binaftil of Formula 33 to a thickness of 600 mm 3. . 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. A light emitting layer was formed by depositing a blue light emitting material doped with 7.5% of a dopant to a thickness of 430 GPa. BAlq [N, N'-bis (naphthalen-1-yl) -N, N'-diphenylbenzidine] of Formula 55 was deposited to a thickness of 20 kPa to form a hole blocking layer. Alq ₃ [tris (8-hydroxyquinolinol)] of Formula 50 was deposited to a thickness of 200 μs to form an electron transport layer. Lithium fluoride (LiF) was deposited to a thickness of 10 GPa to form a buffer 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 14V to the organic light emitting diode manufactured as described above. The applied voltage, current density, luminance and luminous efficiency when the luminous intensity was 1000 cd / m ² were measured, and color coordinates and quantum efficiency were also measured.

[Formula 55]

Comparative Example 2

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

In Comparative Example 2, a hole injection layer was fabricated using a blue light emitting material as a light emitting layer material, and having a thickness (600 μs) of 2-TNATA, which is widely known in the prior art.

2-TNATA [4,4 ', of Formula 4, instead of 4,4'-bis- (3,5-bis- (diphenylamino) -phenyl) -1,1'-binafthyl of Formula 33 An organic light-emitting diode was manufactured and evaluated in the same manner as in Example 6, except that 4 ″ -tris ( N- (2-naphthyl) -N -phenylamino) -triphenylamine] was used as the hole injection layer.

The results of measuring the luminescence properties by fabricating the organic light emitting diode as in the above Example or Comparative Example are shown in Table 3 below, and Table 3 is described again below.

TABLE 3

As the naphthyl derivative according to the present invention, the hole transport material has a high glass transition temperature and a high pyrolysis temperature of 145 ° 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. In particular, when the non-naphthyl derivative of the present invention is used as the hole injection layer in the blue light emission using the blue light emitting material, not only the light emission property is excellent but also the color coordinates hardly occur, so pure blue color can be effectively implemented, so that the total natural color It can be effectively used to fabricate the display device. Therefore, when the organic light emitting diode is manufactured by using the non-naphthyl derivative of the present invention as a hole injection layer, it is possible to simultaneously solve the problems of low light emission luminance and low light emission efficiency, which are the biggest disadvantages of the conventional organic light emitting diode. 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 a full color organic light emitting display device 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 (9)

Vinaphthyl 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 a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group or a substituted or unsubstituted anthryl group. In addition, R1 and R2 May be the same or different from each other and may be directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.) The vinaphthyl derivative represented by the formula (1) is a tetrahalo compound represented by the following formula 11 is represented by the general formula RR'NH (wherein R and R 'represents a hydrocarbon residue) Vinaphthyl derivative, characterized in that it is prepared by reacting with a primary amine. [Formula 11]

(In Formula 11, X ₂ represents a chlorine atom or bromine atom.) The vinaphthyl derivative according to claim 1 or 2, wherein the vinaphthyl derivative represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 33 to 49, in which R1 or R2 is specifically specified. [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]

[Formula 49]

According to claim 2, wherein the secondary amine represented by the general formula RR'NH (wherein R and R 'represents a hydrocarbon residue) is represented by any one of the formulas (16) to (32) derivative. [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] [Formula 31]

[Formula 32]

An organic light emitting diode using the vinapthyl derivative according to claim 1 or 2 as a hole injection material, a hole transport material or a light emitting layer material. Vinaf is represented by Formula 1, characterized by reacting a tetrahalo compound represented by Formula 11 with a secondary amine represented by the general formula RR'NH (wherein R and R 'represent a hydrocarbon residue): Preparation of til derivatives. [Formula 11]

(In Formula 11, X ₂ represents a chlorine atom or bromine atom.) [Formula 1]

(In Formula 1, R1 or R2 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group or a substituted or unsubstituted anthryl group. In addition, R1 and R2 May be the same or different from each other and may be directly connected or connected to each other by an ethylene group, a vinyl group, an oxygen atom or a sulfur atom.) The method of claim 6, wherein the tetrahalo compound is reacted with a secondary amine represented by the general formula RR'NH (wherein R and R 'represent a hydrocarbon moiety) includes a palladium compound and a phosphine compound. A process for producing vinaphthyl derivatives, which is carried out in the presence of a catalyst, a reaction base and a reaction solvent. The method according to claim 6, wherein the tetrahalo compound is reacted with a secondary amine represented by the general formula RR'NH (wherein R and R 'represents a hydrocarbon residue), a copper catalyst and a reaction base or a reaction base and A manufacturing method of vinaphthyl derivative, characterized in that in the presence of a reaction solvent. 8. The method of claim 7, wherein the palladium compound is palladium acetate or tris (dibenzylideneacetone) palladium (0), or the phosphine compound is tri- o -tolylphosphine, 2,2'-bis (diphenylphosphino) -1,1'-vinaphthyl, tri-n-butylphosphine or tri-t-butylphosphine, or the reaction base is a metal alkoxide such as sodium t-butoxide or potassium t-butoxide or reaction solvent Is benzene, toluene, xylene, N, N -dimethylformamide or N, N -dimethylsulfoxide.

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