KR101317881B1 - Aryl amine compounds and organic light-emitting device using the same - Google Patents

Abstract

Provided are an arylamine compound having a phenyl group in which the 2 and 6 positions are substituted with a methyl group, and an organic light emitting device using the same as a hole transport material and / or a hole injection material. This compound has the advantage of high glass transition temperature and low sublimation temperature. Therefore, the compound has excellent thermal stability and good sublimation property to provide easy deposition in fabricating an organic light emitting device. The organic light emitting device of the present invention can be manufactured economically with excellent efficiency and life characteristics by using the aryl amine compound having the above characteristics.

Description

Aryl amine compounds and organic light-emitting device using the same

The present invention relates to an aryl amine compound and an organic light emitting device using the same, and more particularly, to an arylamine compound useful as a hole injection material, a hole transport material or a light emitting material and an organic light emitting device using the same.

Recently, due to the rapid growth of the optical communication and multimedia fields, the development into a highly information society has been accelerated. Accordingly, optoelectronic devices using the change of photons to electrons or the conversion of electrons to photons have become the core of the modern information electronics industry.

The organic light emitting device sandwiches a thin film containing a fluorescent organic compound or a phosphorescent organic compound between the anode and the cathode, and electrons and holes injected from each electrode generate excitons of the fluorescent or phosphorescent compound so that the excitons are in a ground state. It is an element that uses emitted light when it returns.

The electroluminescence phenomenon of these organic materials was reported by Pope et al. In 1963. In 1987, Eastman Kodak et al. (A) showed a multilayer structure with a quantum efficiency of 1% and luminance of 1000 cd / m ² at 10V or less. Since the quinone conjugated structure light emitting device has been reported, many studies have been conducted. They have the advantage of easy synthesis and synthesis of various types of materials and simple color tuning.

Recent advances in the field of organic light emitting devices are remarkable. Among them, high brightness, low emission wavelength, high speed response, and light weight thin device at low applied voltage are noteworthy.

The structure of a general organic light emitting device is a substrate, an anode, a hole injection layer for receiving holes in the anode, a hole transport layer for transporting holes, an electron blocking layer for preventing the entry of electrons from the light emitting layer to the hole transport layer, light by combining holes and electrons It consists of a light emitting layer that emits light, a hole blocking layer that prevents the entrance of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode. Here, the organic layer except for the substrate, the anode and the cathode may be configured in various forms in order to increase the lifetime or efficiency.

Examples of hole transport materials used in conventional organic light emitting devices are US Patent No. 4,720,432, US Patent No. 5,061,569, US Patent No. 6,242,115, Japanese Patent Application Laid-Open No. 11-144873, Japanese Patent Publication No. 2000-302756, Japanese Patent Japanese Patent Laid-Open No. 2006-151979, Japanese Patent Laid-Open No. 2005-290000, Japanese Patent Laid-Open No. 2003-133075, Japanese Patent Laid-Open No. 2004-079265, Korean Patent Laid-Open No. 10-2009-0035729, and the like. However, in order to increase the brightness and large area of the display device, there is a need for improvement in efficiency and lifespan. In addition, as can be seen in the examples of the above patent documents, although the material performance has been improved a lot, the organic light emitting device currently requires higher efficiency and longer life. To meet this, there is a need to significantly improve the performance of existing materials. Representative hole injection materials and / or hole transport materials are NPB (bis (N- (1-naphthyl) -N-phenyl) benzidine), TBPB (N, N, N ', N'-tetrabiphenyl benzidine) and TPD ( 4,4'-bis (tolylphenyl) aminobiphenyl) etc. are mentioned.

Among them, TPD shows a good driving voltage and excellent efficiency, but there is a problem of poor durability due to the low glass transition temperature. NPB shows good sublimation but relatively high driving voltage. Although TBPB exhibits a high glass transition temperature, there is a problem in that workability and process stability are decreased in manufacturing an organic light emitting device due to the high deposition temperature.

Accordingly, one object of the present invention is to provide excellent electrical properties, high glass transition temperature, and sublimation properties, and thus, as a hole injection material or a hole transport material because of its excellent efficiency, thermal stability, and workability and process stability in manufacturing an organic light emitting device. It is to provide useful arylamine compounds.

Another object of the present invention to provide an organic light emitting device excellent in efficiency and life characteristics using the arylamine compound.

Another object of the present invention is to provide an organic light emitting display device employing the organic light emitting device.

In order to achieve the above object, an aspect of the present invention,

It provides an arylamine compound represented by the following formula (1):

[Formula 1]

Here, R ₁ to R ₁₂ may be the same or different from each other, H or an alkyl group having 1 to 5 carbon atoms.

According to an embodiment of the present invention, R ₁ to R ₁₀ may be the same or different from each other, H or a methyl group, R ₁₁ and R ₁₂ may be the same or different from each other, may be H, methyl, or ethyl group.

According to another embodiment of the invention, R ₁ and R ₂ may be the same as R ₃ and R ₄ , respectively, and R ₅ , R ₆ and R ₇ may be the same as each other with R ₈ , R ₉ and R ₁₀ , respectively. have.

In order to achieve the above object, another aspect of the present invention,

Anode; Cathode; And an organic layer interposed between the anode and the cathode.

The organic layer provides an organic light emitting device comprising an arylamine compound according to an aspect of the present invention.

According to another embodiment of the present invention, the organic layer including the arylamine compound may be at least one layer selected from a hole injection layer and a hole transport layer.

According to another embodiment of the invention, the organic layer comprises a light emitting layer, the light emitting layer comprises a host and a dopant, the dopant may be at least one selected from a red phosphorescent compound, a green phosphorescent compound and a blue fluorescent compound have.

In order to achieve the above another object, another aspect of the present invention,

An organic light emitting display device including the organic light emitting diode according to another aspect of the present invention is provided.

The arylamine compounds of the present invention having a phenyl group in which the 2 and 6 positions are substituted with a methyl group exhibit a higher glass transition temperature than the arylamine compound thus unsubstituted. Therefore, the compound is excellent in heat resistance and resistance at high temperatures to joule heat generated between the organic layer and the organic layer and between the organic layer and the electrode in the organic light emitting device. In addition, the arylamine compound of the present invention has a low evaporation temperature and excellent sublimability. Thus, this compound can provide good workability in fabricating an organic light emitting device. The arylamine compound according to the present invention can be usefully used as a hole injection material and a hole transport material. By using the arylamine compound of the present invention, an organic light emitting device having improved luminous efficiency and lifespan can be effectively manufactured.

1 shows a cross-sectional structure of an organic light emitting device according to an embodiment of the present invention.
2 shows a cross-sectional structure of the organic light emitting device manufactured in Example and Comparative Example.
3 is a graph showing a relationship between time and luminance during constant current driving of the organic light emitting diode manufactured in Example 2 and the organic light emitting diodes of Comparative Examples 4 and 5 corresponding to the conventional example. Comparison was made with the initial luminance as 100%.
4 is a graph illustrating a relationship between time and luminance during constant current driving of the organic light emitting diode manufactured in Example 6 and the organic light emitting diode according to Comparative Example 8, which corresponds to a conventional example. Comparison was made with the initial luminance as 100%.

Hereinafter, the arylamine compound of the present invention, the organic light emitting device and the organic light emitting display device using the same are described in more detail.

An arylamine compound according to one aspect of the present invention is represented by the following formula (1):

[Formula 1]

Here, R ₁ to R ₁₂ may be the same or different from each other, H or an alkyl group having 1 to 5 carbon atoms.

The arylamine compound according to one aspect of the present invention has a phenyl group in which the 2 and 6 positions are substituted with a methyl group. The inventors surprisingly found that the arylamine compound having such excellent symmetry shows a higher glass transition temperature than the arylamine compound having no phenyl group substituted at the 2 and 6 positions. Therefore, the arylamine compound of the present invention is excellent in heat resistance and high temperature resistance to joule heat generated between the organic layer and the organic layer and between the organic layer and the electrode in the organic light emitting device. The inventors also found that the arylamine compound has a low evaporation temperature and excellent sublimability while having a high glass transition temperature. Thus, this compound can provide good workability in fabricating an organic light emitting device. The inventors have found in particular that this compound can be usefully used as a hole injection material and a hole transport material. Therefore, by using this arylamine compound, it is possible to economically manufacture the organic light emitting device having improved luminous efficiency and lifespan.

R ₁ to R ₁₀ in Formula 1 may be the same or different from each other, and are H or a methyl group. R ₁₁ and R ₁₂ may be the same or different from each other, and are H, a methyl group, or an ethyl group. R ₁ and R ₂ are the same as R ₃ and R ₄ , respectively, and R ₅ , R ₆ and R ₇ are the same as R ₈ , R ₉ and R ₁₀ , respectively, with high glass transition temperatures, thus high durability and high It is preferable at the point which can show sublimation.

Specific examples of the arylamine compound of Formula 1 include, but are not limited to, Compounds 1 to 16 shown below.

.

.

Hereinafter, an organic light emitting device using an aryl amine compound according to another aspect of the present invention will be described.

The organic light emitting device is an anode; Cathode; And an organic layer interposed between the anode and the cathode, wherein the organic layer includes an aryl amine compound having a phenyl group substituted at the 2 and 6 positions in the methyl group according to an aspect of the present invention. It is a light emitting element. The organic layer including the aryl amine compound may be at least one layer selected from a hole injection layer and a hole transport layer. The organic layer includes a light emitting layer. The light emitting layer includes a host and a dopant. The dopant may be at least one selected from a red phosphorescent compound, a green phosphorescent compound, and a blue fluorescent compound.

The organic light emitting device of the present invention can be manufactured in an economical manner as well as excellent luminous efficiency and lifetime characteristics by using the aryl amine compound having excellent symmetry and compact structure.

The organic light emitting device of the present invention can be realized in various structures. 1 shows a cross-sectional structure of an organic light emitting device according to an embodiment of the present invention. Referring to FIG. 1, an organic light emitting diode 100 according to an embodiment of the present invention includes an anode 2 formed on a transparent substrate 1, a cathode 10, and a light emitting layer 6 interposed therebetween. do. If necessary, one or more layers of the hole injection layer 3, the hole transport layer 4, or the electron blocking layer 5 may be inserted between the anode 2 and the light emitting layer 6. One or more layers of the hole blocking layer 7, the electron transport layer 8, or the electron injection layer 9 may be inserted between the cathode 10 and the light emitting layer 6. However, the structure of the organic light emitting device according to the present invention is not limited thereto. For example, one layer may be formed of the light emitting layer and the electron transporting layer by doping a small amount of fluorescent or phosphorescent dye into the electron transporting layer without forming a separate light emitting layer. The organic layers between the two electrodes 2 and 10 may be formed by a vacuum deposition method, a casting method, or the like.

The anode 2 of the organic light emitting device of the present invention may be formed using a metal, an alloy, an electrically conductive compound or a mixture thereof having a work function of about 4 eV or more. Specifically, transparent conductive materials such as Au or CuI, indium tin oxide (ITO), SnO ₂ and ZnO, which are metals, may be mentioned. The thickness of the anode layer may be about 10-200 nm.

The cathode 10 of the organic light emitting device of the present invention may be formed using a metal, an alloy, an electroconductive compound or a mixture thereof having a work function of less than about 4 eV. Specific examples include aluminum, Na, Na-K alloys, calcium, magnesium, lithium, lithium alloys, indium, aluminum, magnesium alloys, and aluminum alloys. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may be used. Among these, aluminum (Al) which is excellent in stability especially can be used as a cathode. The thickness of the cathode layer may be about 10-200 nm.

In order to increase the luminous efficiency of the organic light emitting device, at least one electrode should preferably have a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundreds of mm 3 / mm or less. The thickness of the electrode is 10 nm to 1 탆, preferably 10 to 400 nm. Such an electrode can be manufactured by forming the electrode material into a thin film by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD) or a sputtering method.

The hole injection layer 3 and / or the hole transport layer 4 may be formed using the aryl amine compound represented by Chemical Formula 1. In addition, within the content range that does not impair the effects of the present invention, a material commonly used as a hole transport material in the photoconductive material and a known material used for forming the hole transport layer or hole injection layer of the organic light emitting device is further included. Can be. For example, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (hereinafter referred to as TPD), N, N'-bis (1- Naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (hereinafter referred to as NPD), N, N'-diphenyl-N, N'-dinaphthyl -4,4'-diaminobiphenyl, N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N, N'N'-tetraphenyl-4, 4'-diaminobiphenyl; Porphyrin compound derivatives such as Copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; Polymers having aromatic tertiary amines in the main or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (p-tolyl) amine, 4 ', 4' Triarylamine derivatives such as 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as metal phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamnstilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilanes.

The electron blocking layer 5 may be formed using fac-tris (1-phenylpyrazolato, N, C2 ') iridium (III) (Irppz).

The light emitting layer 6 may include a host and a dopant. The light emitting layer 6 may further include at least one of a phosphorescent host, a fluorescent host, and a dopant in the visible light region. The dopant may be at least one selected from a red phosphorescent compound, a green phosphorescent compound, and a blue fluorescent compound. It may also be formed using known light emitting materials, for example, photoluminescent fluorescent materials, fluorescent brighteners, laser dyes, organic scintillators and fluorescence reagents. Specific examples include polyaromatic compounds such as AlQ ₃ , anthracene, phenanthrene, pyrene, Kirisen, perylene, coronene, rubrene, and quinakiridone; Oligophenylene compounds such as quiterphenyl; 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1 , 4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-t-butyl-2-oxazolyl) benzene, 1,4-diphenyl 1,3-butadiene, 1,6 Scintillator for liquid scintillation such as -diphenyl-1,3,5-hexatriene-1,1,4,4-tetraphenyl-1,3-butadiene; Metal complexes of auxin derivatives; Coumarin pigments; Dicyano methylene pyran pigment; Dicyano methylenethiopyran pigments; Polymethine pigments; Oxo benzanthracene pigments; Xanthene pigments; Carbostyryl pigments; Perylene pigments; Oxazine compounds; Stilbene derivatives; Spiro compounds; An oxadiazole compound etc. are mentioned.

The hole blocking layer 7 includes 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,4'-bis (9-carbazolyl) -biphenyl (CBP), At least one selected from BAlq and allyl phosphine compounds described in Applicant's patent application 2004-0054699.

The electron transport layer 8 is preferably a material having a high electron mobility capable of receiving electrons from the electron injection layer 9 and transferring the electrons to the light emitting layer 6 well. The electron transport layer 8 and the electron injection layer 9 can be arbitrarily selected from materials commonly used as electron transport materials among photoconductive materials and known materials used in the electron transport layer or electron injection layer of organic EL devices. . Specific examples of such electron transfer compounds include imidazole derivatives, oxadiazole compounds, triazole derivatives, phenylenediamine derivatives, stilbene derivatives, styryl anthracene derivatives, fluorene derivatives, hydrazone derivatives, diphenylquinone derivatives, Perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, metal complexes of oxine derivatives, polymers of quinoxaline derivatives, phenanthroline derivatives and the like. Specifically, in one embodiment of the present invention, the electron transport layer 8 includes 8-hydroxyquinoline aluminum complex (AlQ ₃ ); AlQ ₃ Organic compounds including structures; Hydroxyflavone-metal complexes; Silacyclopentadiene (silole) compounds; It may be formed of an allyl phosphine compound. The electron injection layer 9 may be formed of an aryl phosphine compound described in the applicant's patent application No. 2007-32969, a metal complex such as lithium quinolate or an inorganic substance such as LiF.

The organic layers are supported by the transparent substrate 1. The material of the transparent substrate 1 is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For example, glass, such as an alkali free borosilicate glass, a transparent plastic film, etc. can be used.

Each organic layer or inorganic layer constituting the organic light emitting device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or laser thermal transfer. There is no particular limitation on the film thickness of each layer, and may be appropriately selected depending on the properties of the material, but may be determined in the range of 2 to 5,000 nm, preferably 10 to 2500 nm.

The method of manufacturing an organic light emitting device using the arylamine-based compound of the present invention as a hole injection material and / or a hole transport material is an organic material of the anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode structure The light emitting device is described as an example.

First, a hole injection layer is formed using a hole injection material on an ITO transparent substrate having a thickness of 1 μm or less, preferably 10 to 200 nm. Subsequently, the hole transport layer is formed using the aryl amine compound represented by Chemical Formula 1 according to the present invention. Subsequently, the light emitting layer is formed so as to cover the hole transport layer by vacuum depositing a fluorescent or phosphorescent dopant with the host. Subsequently, an electron transport layer is formed on the emission layer by using the electron transport material. Subsequently, an electron injection layer is formed on the electron transport layer by using an electron injection material. Finally, the electron injection layer is coated with a thin film containing a cathode material with a thickness of 1 μm or less to obtain a cathode, thereby obtaining an organic light emitting device. When the DC voltage is applied to the organic light emitting device obtained by using the anode as the positive electrode and the cathode as the negative electrode, light emission can be observed through the transparent or opaque electrode (either the anode or the cathode, or both electrodes).

Hereinafter, a method of manufacturing an organic light emitting device having an aryl amine compound and a hole transport layer and / or a hole injection layer formed using the same according to the present invention will be described in more detail. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

Example

Synthetic example  1: Synthesis of compound 1

(Synthesis of Intermediate 1)

In a nitrogen atmosphere, 25 g of 2,7-dibromofluorene and 35 g of KOH were dissolved in 350 ml of DMSO, cooled to 0 ° C., and 60 ml of distilled water was slowly added to the reaction mixture over 20 minutes. After stirring for 1 hour at the same temperature, 44g of iodine methane was added and the temperature was gradually raised to room temperature and stirred for 15 hours. 500 ml of distilled water was added to the reaction product to terminate the reaction, and the precipitated solid was filtered, dried and purified by column chromatography to give 21 g of a white solid (yield: 77.5%).

(Synthesis of Intermediate 3)

17 g of 3-bromotoluene and 18.2 g of 2,6-dimethylaniline were dissolved in 70 ml of toluene under a nitrogen atmosphere. To this mixture, 0.5 g of (t-Bu) ₃ P, 0.13 g of Pd (OAc) ₂ and 19 g of t-BuONa were added, stirred at room temperature for 30 minutes, and heated and refluxed. After refluxing for 4 hours, the reaction was terminated by adding excess water. Intermediate 3 was extracted with diethyl ether, water was removed with anhydrous magnesium sulfate, and then the solvent was removed. Purification by column chromatography gave 16 g of a pale yellow liquid material (yield: 75%).

(Synthesis of Compound 1)

5.28 g of Intermediate 1 and 6.3 g of Intermediate 3 were dissolved in 50 ml of toluene under a nitrogen atmosphere, and then 0.2 g of (t-Bu) ₃ P, 0.05 g of Pd (OAc) ₂ , and 4.8 g of t-BuONa were added thereto. After stirring for minutes, it was heated and refluxed. After refluxing for 4 hours, the reaction was terminated by adding excess water. Extraction was carried out with diethyl ether, water was removed with anhydrous magnesium sulfate, and the solvent was removed. Purification by column chromatography gave 4.5 g of a pale yellow solid (yield: 49%).

Mass spectrum; m / e = 612 (M < + >).

NMR- ¹ H (500 MHz, CDCl 3; ppm): δ = 1.31 (s, 6H), 2.03 (s, 12H), 2.23 (s, 6H), 6.69, 6.75, 6.82 (t, 8H), 7.06-7.16 ( m, 10H), 7.36 (s, 2H).

Synthetic example  2: synthesis of compound 3

(Synthesis of Intermediate 5)

Synthesis of Intermediate 3 in Synthesis Example 1, except that 26.4 g of 4-bromo-o-xylene (70%) was used instead of 3-bromotoluene and In the same manner, 12.3 g of a pale yellow liquid was synthesized (yield: 53.3%).

(Synthesis of Compound 3)

In Synthesis Example 1 (Synthesis of Compound 1), 6.7 g of Intermediate 5 instead of Intermediate 3 was synthesized in the same manner as described for (Synthesis of Compound 1), to obtain 4 g of a pale yellow solid (yield: 41.7%) .

Mass spectrum; m / e = 640 (M < + >).

NMR- ¹ H (500 MHz, CDCl 3; ppm): δ = 1.31 (s, 6H), 2.03 (s, 12H), 2.14 (s, 12H), 6.70, 6.81 (d, 5H), 6.95 (s, 3H) , 7.11 (s, 8 H), 7.33 (s, 2 H).

Synthetic example  3: (synthesis of compound 4)

(Synthesis of Intermediate 6)

Synthesis of Intermediate 3 in Synthesis Example 1, except that 18.5 g of 1-bromo-3,5-dimethylbenzene was used instead of 3-bromotoluene to obtain 15 g of a pale yellow solid (yield: 66.7%).

(Synthesis of Compound 4)

In the same manner as in Synthesis 1 (Synthesis of Compound 1), 6.7 g of Intermediate 6 was used instead of Intermediate 3 to obtain 5.2 g of a pale yellow solid (yield: 54.2%).

Mass spectrum; m / e = 640 (M < + >).

NMR- ¹ H (500 MHz, CDCl 3; ppm): δ = 1.31 (s, 6H), 2.03 (s, 12H), 2.19 (s, 12H), 6.53 (s, 2H), 6.61 (s, 4H), 6.73 (s, 2H), 7.10-7.16 (m, 8H), 7.35 (s, 2H).

Synthetic example  4: (synthesis of compound 5)

(Synthesis of Intermediate 7)

Synthesis was carried out in the same manner as in Synthesis Example 1 (Synthesis of Intermediate 3), except that 20.3 g of 2,4,6-thimethylmethylarline was used instead of 2,6-dimethylaniline to obtain 14 g of a liquid pale yellow substance. Yield: 62.2%).

(Synthesis of Compound 5)

4.9 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (synthesis of Compound 1) except that 6.7 g of Intermediate 7 was used instead of Intermediate 3 (yield: 52%).

Mass spectrum; m / e = 640 (M < + >).

NMR- ¹ H (500 MHz, CDCl 3; ppm): δ = 1.31 (s, 6H), 1.99 (s, 12H), 2.23 (s, 6H), 2.33 (s, 6H), 6.74-6.82 (m, 7H) , 6.93 (s, 5H), 7.07 (s, 4H), 7.35 (s, 2H).

Synthetic example  5: (synthesis of compound 7)

(Synthesis of Intermediate 10)

In Synthesis Example 1 (Synthesis of Intermediate 3), 20.3 g of 2,4,6-trimethylaryline was used instead of 2,6-dimethylaniline and 26.4 g of 4-bromo-o-xylene was substituted for 3-bromotoluene. Synthesis was carried out in the same manner except using (70%), to obtain 18.6 g of a pale yellow solid (yield: 78%).

(Synthesis of Compound 7)

Synthesis was carried out in the same manner as in Synthesis 1 of Synthesis 1, except that 7.2 g of Intermediate 10 was used instead of Intermediate 3 to obtain 4.3 g of a pale yellow solid (yield: 43.2%).

Mass spectrum; m / e = 668 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.30 (s, 6H), 1.99 (s, 12H), 2.15 (s, 6H), 2.19 (s, 6H), 2.32 (s, 6H), 6.69, 6.70 (d, 4H), 6.82 (s, 2H), 6.92 (s, 4H), 6.93, 6.95 (d, 2H), 7.10 (s, 2H), 7.32, 7.34 (d, 2H).

Synthetic example  6: Synthesis of Compound 13

(Synthesis of Intermediate 11)

In Synthesis Example 1 (Synthesis of Intermediate 3), 16 g of 3-methylaryline was used instead of 2,6-dimethylaniline and 21.3 g of 1-bromo-2,3,5,6- instead of 3-bromotoluene Synthesis was carried out in the same manner except that tetramethylbenzene was used to obtain 15.5 g of a pale yellow solid (yield: 65%).

(Synthesis of Compound 13)

4.86 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (Synthesis of Compound 1), except that 7.2 g of Intermediate 11 was used instead of Intermediate 3. (Yield 48.5%).

Mass spectrum; m / e = 668 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.30 (s, 6H), 1.95 (s, 12H), 2.23 (s, 18H), 6.67, 6.72 (d, 6H), 6.84 (s, 2H ), 6.97 (s, 2H), 7.05, 7.07, 7.08 (t, 2H), 7.20 (s, 2H), 7.33 (s, 2H).

Synthetic example  7: Synthesis of Compound 14

(Synthesis of Intermediate 12)

In Synthesis Example 1 (Synthesis of Intermediate 3), 16 g of 4-methylaryline was used instead of 2,6-dimethylaniline and 21.3 g of 1-bromo-2,3,5,6- instead of 3-bromotoluene Synthesis was carried out in the same manner except that tetramethylbenzene was used to obtain 16 g of a pale yellow solid (yield: 66.8%).

(Synthesis of Compound 14)

Synthesis was carried out in the same manner as in Synthesis 1 of Synthesis 1, except that 7.2 g of Intermediate 12 was used instead of Intermediate 3 to obtain 4.5 g of a pale yellow solid (yield: 45%).

Mass spectrum; m / e = 668 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.32 (s, 6H), 1.95 (s, 12H), 2.22 (s, 12H), 2.27 (s, 6H), 6.64, 6.66 (d, 2H) ), 6.88-6.91 (m, 4H), 6.96-7.0 (m, 6H), 7.14 (s, 2H), 7.31, 7.32 (d, 2H).

Synthetic example  8: Synthesis of Compound 16

(Synthesis of Intermediate 13)

In Synthesis Example 1 (Synthesis of Intermediate 3), 18.2 g of 3,5-dimethylaniline was used instead of 2,6-dimethylaniline and 21.3 g of 1-bromo-2,3,5, instead of 3-bromotoluene Synthesis was carried out in the same manner except that 6-tetramethylbenzene was used to obtain 15.9 g of a pale yellow solid (yield: 63%).

(Synthesis of Compound 16)

5.4 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (Synthesis of Compound 1), except that 7.6 g of Intermediate 13 was used instead of Intermediate 3 (yield: 51.6%).

Mass spectrum; m / e = 696 (M < + >).

NMR- ¹ H (500 MHz, CDCl 3; ppm): δ = 1.33 (s, 6H), 1.95 (s, 12H), 2.19 (s, 12H), 2.23 (s, 12H), 6.51 (s, 2H), 6.60 (s, 6H), 6.96 (s, 2H), 7.22 (s, 2H), 7.31, 7.33 (d, 2H).

Synthetic example  9: Synthesis of Compound 17

(Synthesis of intermediate 2)

18 g of a white solid was obtained in the same manner as in Synthesis Example 1 (synthesis of Intermediate 1), except that 48 g of iodine ethane was used instead of iodine methane (yield: 61.5%).

(Synthesis of Compound 17)

5 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (Synthesis of Compound 1), except that 5.7 g of Intermediate 2 was used instead of Intermediate 1 (yield: 52%).

Mass spectrum; m / e = 640 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 0.37, 0.39, 0.40 (t, 6H), 1.77, 1.78, 1.80, 1.81 (dd, 4H), 2.04 (s, 12H), 2.23 (s, 6H), 6.71 (s, 4H), 6.82 (s, 2H), 7.06-7.16 (m, 10H), 7.35 (s, 2H).

In the following Synthesis Examples 10 to 12 will be described in detail the synthesis method of the compound 21 to 23 which is an aryl amine compound to be used in the comparative example.

Synthetic example  10: Synthesis of Compound 21

 (Synthesis of Intermediate 14)

Synthesis was carried out in the same manner as in Synthesis Example 1 (Synthesis of Intermediate 3), except that 13.9 g of aniline was used instead of 2,6-dimethylaniline and 17.1 g of 2-bromotoluene was used instead of 3-bromotoluene. 13.7 g of a pale yellow solid was obtained (yield: 75%).

(Synthesis of Compound 21)

5.3 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (Synthesis of Compound 1), except that 5.5 g of Intermediate 14 was used instead of Intermediate 3 (yield: 63.4%).

Mass spectrum; m / e = 556 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.30 (s, 6H), 2.03 (s, 6H), 6.90 (s, 4H), 6.96, 6.98 (d, 4H), 7.04 (s, 2H ), 7.13-7.24 (m, 12H), 7.40 (s, 2H).

Synthetic example  11: Synthesis of Compound 22

(Synthesis of Intermediate 15)

14.1 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (synthesis of Intermediate 3), except that 13.9 g of aniline was used instead of 2,6-dimethylaniline (yield: 77%).

(Synthesis of Compound 22)

5.1 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (Synthesis of Compound 1), except that 5.5 g of Intermediate 15 was used instead of Intermediate 3 (yield: 61%).

Mass spectrum; m / e = 556 (M < + >).

MR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.30 (s, 6H), 2.22 (s, 6H), 6.90 (s, 4H), 6.97, 6.98 (d, 4H), 7.06 (s, 2H ), 7.22-7.26 (m, 12H), 7.41 (s, 2H).

Synthetic example  12: Synthesis of Compound 23

(Synthesis of Intermediate 16)

Synthesis was carried out in the same manner as in Synthesis Example 1 (synthesis of Intermediate 3), except that 13.9 g of aniline was used instead of 2,6-dimethylaniline and 18.5 g of 3,5-dimethylbenzene was used instead of 3-bromotoluene. To yield 13.8 g of a pale yellow solid (yield: 70%)

(Synthesis of Compound 22)

4.5 g of a pale yellow solid was obtained in the same manner as in Synthesis Example 1 (synthesis of Compound 1) except that 5.9 g of Intermediate 16 was used instead of Intermediate 3 (yield: 52%).

Mass spectrum; m / e = 584 (M < + >).

NMR- ¹ H (500 MHz, CDCl ₃ ; ppm): δ = 1.34 (s, 6H), 2.21 (s, 12H), 6.66 (s, 2H), 6.74 (s, 4H), 6.96, 6.98, 6.99 (t , 4H), 7.09, 7.10 (d, 4H), 7.14 (s, 2H), 7.21-7.25 (m, 4H), 7.46, 7.47 (d, 2H).

Table 1 below summarizes the physical properties of several compounds obtained in the above synthesis examples.

matter Melting point
(℃) Glass transition temperature
(℃) Sublimation Temperature (℃)
(@ 1.0 torr) Compound 1 231 91 220-230 Compound 3 254 109 240-250 Compound 4 247 113 235-245 Compound 5 266 101 250-260 Compound 17 212 81 235-245 NPB 280 101 320 ~ 330 TPD 172 71 210-220 TBPB 266 136 340-350 Compound 21 141 78 260-265 Compound 22 194 78 260-265 Compound 23 216 91 260-265

Referring to Table 1, the aryl amine compound of the present invention has a similar chemical structure except that NPB, TPD, and TBPB, which are materials used for manufacturing a conventional glass light emitting device, as well as the 2,6 position are not substituted with a methyl group. It can be seen that the sublimation temperature is low while the glass transition temperature is high compared to the aryl amine compound of Formula 21 to 23 having. Therefore, by using the aryl amine compound of the present invention it is possible to implement an organic layer that can be deposited economically while having high thermal stability.

Example  1: Fabrication of Organic Light-Emitting Device Using Compound 1

This example is to explain the fabrication of an organic light emitting device using Compound 1 obtained in Synthesis Example 1 as the hole transport material of the hole transport layer.

First, an OLED glass having a transparent electrode ITO thin film (surface specific resistance: 10 Ω / □) was ultrasonically washed with distilled water, isopropyl alcohol, and methylene chloride sequentially, and then dried using an inert gas.

Next, OLED glass is installed on the substrate holder of the vacuum deposition equipment, and LGC101 (manufacturer: LG Chemical) is vacuum-deposited on the ITO thin film at a speed of 0.5-2.0 Å / sec under a vacuum of 1ⅹ10-6torr to inject a hole of 10 nm in thickness. A layer was formed. Subsequently, NPB was vacuum deposited on the hole injection layer at a rate of 0.5˜2.0 μs / sec to form a first hole transport layer having a thickness of 100 nm. Compound 1 was vacuum deposited on the first hole transport layer to form a second hole transport layer having a thickness of 60 nm. Subsequently, a light emitting layer having a thickness of 40 nm was formed by depositing and doping BAlq, which is a light emitting host material, and red light emitting dopant material Ir (piq) 3, at different rates. The doping amount of the light emitting layer was adjusted to 10 wt% BAlq and 90 wt% Ir (piq) 3. Subsequently, Alq3 was deposited to a thickness of 30 nm as the electron transport layer on the light emitting layer, and then Liq was deposited to a thickness of 5 nm as the electron injection layer. Subsequently, Al was formed into a cathode layer of 100 nm to complete the organic light emitting device. The completed organic light emitting device showed an efficiency of 10.55 lm / w at a voltage density of 4.83 volt and 10mA / cm2.

Example 2

This Example is to explain the fabrication of an organic light emitting device using Compound 4 obtained in Synthesis Example 3 as the hole transport material of the second hole transport layer.

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1 as the second hole transport layer. The completed organic light emitting diode showed an efficiency of 11.90 lm / w at a voltage density of 4.63 volts and a current density of 10 mA / cm2.

Example 3

This example is to explain the fabrication of an organic light emitting device using Compound 1 obtained in Synthesis Example 1 as the hole transport material of the first hole transport layer.

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 1 was used instead of NPB as the first hole transport layer material. The finished organic light emitting device showed an efficiency of 10.24 lm / w at a voltage density of 4.31 volts and 10mA / cm2.

Comparative Example 1

An organic light emitting diode was manufactured according to the same method as Example 1 except for using TBPB as the second hole transport layer material. The completed organic light-emitting device showed an efficiency of 14.90 lm / w at a voltage density of 4.85 volt and current density of 10 mA / cm2.

Comparative Example 2

An organic light-emitting device was manufactured in the same manner as in Example 1, except that NPB was used as the second hole transport layer material. The finished organic light emitting device showed an efficiency of 7.93 lm / w at a voltage density of 5.98 volts and a current density of 10 mA / cm2.

Comparative Example 3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using TPD as the second hole transport layer material. The completed organic light emitting device showed an efficiency of 7.20 lm / w at a voltage density of 5.82 volts and a current density of 10 mA / cm2.

Comparative Example 4

An organic EL device was manufactured in the same manner as in Comparative Example 1, except that TBPB was used as the first hole transport layer. The completed organic light emitting device showed an efficiency of 8.99 lm / w at a voltage density of 4.76 volts and a current density of 10 mA / cm2.

Comparative Example 5

An organic EL device was manufactured in the same manner as in Example 1, except that Compound 22 obtained in Synthesis Example 11 was used as the second hole transport layer material. The completed organic light emitting diode showed an efficiency of 11.07 lm / w at a voltage density of 4.79 volts and a current density of 10 mA / cm2.

Comparative Example 6

An organic EL device was manufactured in the same manner as in Example 1, except that Compound 21 obtained in Synthesis Example 10 was used as the second hole transport layer material. The completed organic light emitting diode showed efficiency of 9.37 lm / w at 5.36 volt and 10mA / cm2 current density.

Comparative Example 7

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 23 obtained in Synthesis Example 12 was used as the second hole transport layer material. The completed organic light emitting device showed an efficiency of 10.55 lm / w at a voltage density of 4.70 volts and 10mA / cm2.

Table 2 summarizes the evaluation result of the organic light emitting element produced in Examples 1-3 and Comparative Examples 1-7.

@ 10mA / cm2 1st
Hole transport layer
matter Second
Hole transport layer
matter Luminous efficiency
(cd / A) Power efficiency
(lm / W) Color coordinates
(x, y) Driving voltage
(Volt) Example 1 NPB Compound 1 16.25 10.55 (0.67, 0.32) 4.83 Example 2 NPB Compound 4 17.55 11.90 (0.67, 0.32) 4.63 Example 3 Compound 1 Compound 1 14.08 10.24 (0.67, 0.32) 4.31 Comparative Example 1 NPB TBPB 14.90 9.64 (0.67, 0.32) 4.85 Comparative Example 2 NPB NPB 15.12 7.93 (0.67, 0.32) 5.98 Comparative Example 3 NPB TPD 13.41 7.20 (0.67, 0.32) 5.82 Comparative Example 4 TBPB TBPB 13.65 8.99 (0.67, 0.32) 4.76 Comparative Example 5 NPB Compound 22 16.90 11.07 (0.67, 0.32) 4.79 Comparative Example 6 NPB Compound 21 16.02 9.37 (0.67, 0.32) 5.36 Comparative Example 7 NPB Compound 23 15.81 10.55 (0.67, 0.32) 4.70

Example 4

This example is to explain the fabrication of an organic light emitting device using Compound 1 obtained in Synthesis Example 1 as the hole transport material of the hole transport layer.

To this end, 80 nm thick is deposited using Compound 1 as the first hole transport layer material, and 20 nm thick NPB is formed as the second hole transport layer material, followed by DNA (9,10-di- (1-naph) as a light emitting host material. Til) anthracene) and blue light emitting dopant material 1,6-bisdiphenylaminopyrene were deposited and doped at different rates to form a 40 nm thick light emitting layer. At this time, the doping amount of the light emitting layer was adjusted to be 96% by weight of DNA and 4% by weight of 1,6-bisdiphenylaminopyrene. Except for this, an organic light emitting device was manufactured in the same manner as in Example 1. The completed organic light emitting device showed an efficiency of 4.79 lm / w at a voltage density of 4.23 volts and a current density of 10 mA / cm2.

Example 5

This example is to explain the fabrication of an organic light emitting device using Compound 4 obtained in Synthesis Example 3 as the hole transport material of the hole transport layer. An organic light emitting device was manufactured in the same manner as in Example 4, except that Compound 4 was used instead of Compound 1 as the first hole transport layer material. The completed organic light emitting device showed an efficiency of 4.76 lm / w at a voltage density of 4.43 volts and a current density of 10 mA / cm2.

Example 6

This example is to explain the fabrication of an organic light emitting device using Compound 5 obtained in Synthesis Example 4 as the hole transport material of the hole transport layer. An organic light emitting device was manufactured in the same manner as in Example 4, except that Compound 5 was used instead of Compound 1 as the first hole transport layer material. The finished organic light emitting device showed an efficiency of 5.19 lm / w at a voltage density of 4.63 volts and a current density of 10 mA / cm2.

Comparative Example 8

An organic light emitting device was manufactured in the same manner as in Example 4, except that NPB was used as the first hole transport layer material. The completed organic light emitting device showed an efficiency of 4.55 lm / w at a voltage density of 4.45 volts and a current density of 10 mA / cm2.

Comparative Example 9

An organic light emitting device was manufactured in the same manner as in Example 4, except that TPD was used as the first hole transport layer material and TPD was also used as the second hole transport layer material. The completed organic light emitting diode showed an efficiency of 2.04 lm / w at a voltage density of 6.27 volts and a current density of 10 mA / cm2.

Table 3 below summarizes the evaluation results of the organic light-emitting device produced in Examples 4-6 and Comparative Examples 1-2.

@ 10mA / cm2 1st hole transport layer
matter 2nd hole transport layer
matter Luminous efficiency
(cd / A)
@ 10 mA / cm ² Power efficiency
(lm / W)
@ 10mA / cm2 Color coordinates
(x, y) Driving voltage
(V) Example 4 Compound 1 NPB 6.47 4.79 (0.13, 0.19) 4.23 Example 5 Compound 4 NPB 6.74 4.76 (0.13, 0.19) 4.43 Example 6 Compound 5 NPB 7.66 5.19 (0.13, 0.19) 4.63 Comparative Example 8 NPB NPB 6.45 4.55 (0.13, 0.19) 4.45 Comparative Example 9 TPD TPD 6.08 2.04 (0.13, 0.18) 6.27

As can be seen in the above synthesis examples, the arylamine compound of the present invention having a phenyl group substituted at position 2 and 6 shows a higher melting point and glass transition temperature than the unsubstituted compound. . Nevertheless, the compound shows a low sublimation temperature, indicating that the compound is excellent in sublimation.

In addition, referring to Tables 2 and 3, the organic light emitting device manufactured by using the organic light emitting compound of the present invention as a hole transporting material is more efficient and lifespan than the organic light emitting device manufactured using conventional TPD, NPB, and TBPB. It can be seen that the characteristics are excellent.

3 is a graph showing a relationship between time and luminance during constant current driving of the organic light emitting diode manufactured in Example 2 and the organic light emitting diodes of Comparative Examples 4 and 5 corresponding to the conventional example. 4 is a graph showing the relationship between time and luminance during constant current driving of the organic light emitting device manufactured in Example 6 and the organic light emitting device of Comparative Example 8, which corresponds to a conventional example. 3 and 4, an organic light emitting device manufactured using the aryl amine compound of the present invention as a hole transporting material is compared with an organic light emitting device manufactured using conventional NPB, TBPB, and compound 22 as the hole transporting material. It can be seen that it can provide high life characteristics.

100: organic light emitting device 1: transparent substrate
2: anode 3: hole injection layer
4: hole transport layer 5: electronic blocking layer
6: light emitting layer 7: hole blocking layer
8: electron transport layer 9: electron injection layer
10: cathode

Claims (8)

An arylamine compound represented by the following formula (1): < EMI ID =
[Formula 1]

Here, R ₁ to R ₁₂ may be the same or different from each other, H or an alkyl group having 1 to 5 carbon atoms. The aryl according to claim 1, wherein R ₁ to R ₁₀ may be the same or different from each other, and are H or a methyl group, and R ₁₁ and R ₁₂ may be the same or different from each other, and are H, a methyl group, or an ethyl group. Amine compounds. The aryl according to claim 1, wherein R ₁ and R ₂ are the same as each other with R ₃ and R _4, and R ₅ , R ₆ and R ₇ are the same as each other with R ₈ , R ₉ and R ₁₀ , respectively. Amine compounds. The arylamine compound according to claim 1, wherein the organic light emitting compound of Formula 1 is selected from Compounds 1 to 20 shown below:

. Anode; Cathode; And an organic layer interposed between the anode and the cathode.
An organic light-emitting device in which the organic layer comprises the arylamine compound according to any one of claims 1 to 4. The organic light emitting device of claim 5, wherein the organic layer including the arylamine compound is at least one layer selected from a hole injection layer and a hole transport layer. The organic light emitting diode of claim 5, wherein the organic layer comprises a light emitting layer, and the light emitting layer comprises a host and a dopant, and the dopant is at least one selected from a red phosphorescent compound, a green phosphorescent compound, and a blue fluorescent compound. device. An organic light emitting display device comprising the organic light emitting diode of claim 5.

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