WO2016150193A1

WO2016150193A1 - Organic electroluminescent material and device prepared thereby

Info

Publication number: WO2016150193A1
Application number: PCT/CN2015/096421
Authority: WO
Inventors: 高春吉; 崔敦洙; 汪康; 孙毅
Original assignee: 吉林奥来德光电材料股份有限公司
Priority date: 2015-03-24
Filing date: 2015-12-04
Publication date: 2016-09-29
Also published as: CN104829520B; CN104829520A

Abstract

A novel aromatic amine derivative of the present invention is formed in a manner that a bis-carbazole compound links to Ar₁ and Ar₂ through ether bonds, and is capable of rising electron intensity and increase relevant properties, and in addition, the novel aromatic amine derivative of the present invention has the advantages of regulating molecular weight and varieties about R₁ and R₄ ligands of bis-carbazole, improving the performance, improving functions, and the like. An organic device using an amine derivate of the present invention has high brightness, excellent heat resistance, long service life and high efficiency, a synthesis and purification process is simpler, the cost is low, and the requirements on industrial production can be met.

Description

Organic electroluminescent material and device prepared from the same

The present application claims priority to Chinese Patent Application No. 201510128210.3, entitled "Organic Electroluminescent Materials and Devices for the Preparation of the Organic Electroluminescent Materials", which is filed on March 24, 2015. The entire contents are incorporated herein by reference.

Technical field

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. Specifically, it relates to novel aromatic compounds as electroluminescent materials and uses them as an organic electroluminescent device.

Background technique

An organic electroluminescent device generally consists of two opposing electrodes and at least one layer of an organic luminescent compound interposed between the two electrodes. Charge is injected into the organic layer formed between the anode and the cathode to form electron and hole pairs, causing light emission of an organic compound having fluorescent or phosphorescent properties.

Organic electroluminescent device (OLED) is a new type of flat display device with energy saving, fast response, stable color, strong environmental adaptability, no radiation, long life, light weight and thin thickness. Due to the rapid development of optoelectronic communication and multimedia in recent years, organic optoelectronic materials have become the core of the modern social information and electronics industry.

At present, the host material in the electroluminescent device mainly has two types of small molecule host materials and polymer host materials. Many high-efficiency electroluminescent devices have been prepared by doping a phosphorescent complex with a small molecule host material as a light-emitting layer. However, the preparation of small molecule electroluminescent devices requires complex processes such as vacuum evaporation, which greatly increases the manufacturing cost. At the same time, the nature of the small molecule itself is easy to crystallize and the stability of the device is greatly limited. In recent years, the preparation of electroluminescent devices by doping various phosphorescent complex guest bodies with a polymer host material as a light-emitting layer has received much attention. However, the polymer host material which has been reported so far has relatively poor solubility and film forming properties, thereby affecting it as a light-emitting layer. The technology of the present invention is a technology related to organic electro-device materials. Currently, representative materials of hole transport materials in organic electro-devices are as follows:

The characteristics of the currently required materials are that the material has thermal stability and rapid hole mobility, and the high efficiency and long life of the illuminant. The present invention provides a material superior in performance to the present stage.

Summary of the invention

The invention provides a hole transporting material with good luminous efficiency, which connects a biscarbazole and an ether compound together, increases the mobility of holes, and prepares the new aromatic amine compound into a device. Very good luminous efficiency.

According to the technical solution of the present invention, the structural formula of the novel aromatic amine derivative is

[Chemical Formula 1]

In the above Chemical Formula 1, L ₁ is an integer of 0 to 2, and Ar ₁ is an aryl group having 6 to 30 carbon atoms (arylene group when L ₁ > 0, but does not include a benzo compound), and Ar ₂ is a carbon number. a substituted aralkyl group of 7 to 50, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a carbon number of 5 to 50. a heterocyclic, substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

R ₁ to R ₄ represent the same or different hydrogen atoms, substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, substituted or unsubstituted a substituted aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, and a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms. Aromatic amines.

The biscarbazole derivative is a novel aromatic amine compound specific to any one of the following Chemical Formula 2-1 to Chemical Formula 2-5:

[Chemical Formula 2-1] When R ₁ to R ₄ are hydrogen,

[Chemical Formula 2-2] When R ₂ to R ₄ are hydrogen,

[Chemical Formula 2-3] When R ₃ and R ₄ are hydrogen,

[Chemical Formula 2-4] When R ₁ and R ₄ are hydrogen,

[Chemical Formula 2-5] When R ₁ to R ₄ are both hydrogen or not hydrogen,

In Chemical Formula 2-1 to Chemical Formula 2-5, L ₁ is an integer of 0 to 2, Ar ₁ is an aryl group having 6 to 30 carbon atoms (arylene group when L ₁ >0), and Ar ₂ is a carbon atom number 7 ～50 aralkyl group, aralkyloxy group having 7 to 50 carbon atoms, aralkyl fluorenyl group having 7 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, heterocyclic ring having 5 to 50 carbon atoms, A substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.

R ₁ to R ₄ represent a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, and a substituted or unsubstituted carbon atom number of 7 to 50. An aralkyl fluorenyl group, an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.

The chemical formula 1 includes a specific new aromatic amine compound specific to any one of the following Chemical Formulas 3-1 to 3-8:

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Chemical Formula 3-4]

[Chemical Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

In the above Chemical Formula 3-1 to Chemical Formula 3-8, Ar ₂ is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, or carbon. An aryl group having 6 to 50 atoms, a heterocyclic ring having 5 to 50 carbon atoms, or an aromatic amine having 6 to 30 carbon atoms which are substituted or unsubstituted.

L ₁ is an integer of 0 to 2, and R ₁ to R ₄ represent the same or different hydrogen atoms, substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, and substituted or unsubstituted carbon atoms 7 to 50. Aralkyloxy group, substituted or unsubstituted aralkyl fluorenyl group having 7 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, substituted or unsubstituted A substituted aromatic amine having 6 to 30 carbon atoms.

In the above Chemical Formula 1, Chemical Formula 2-1 to 2-5, and Chemical Formula 3-1 to 3-8, R ₁ to R _{4 are} selected from any one of the following chemical formulae to constitute a specific new aromatic amine compound:

Wherein X and Y independently represent an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and a substitution. Or an unsubstituted aralkyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a substituted or unsubstituted A substituted heterocyclic group having 5 to 30 carbon atoms or a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.

The chemical formula 1 described above can be expressed as any one of the following chemical formulas 4-1 to 4-6 to represent a specific new aromatic Aromatic amine compound.

[Chemical Formula 4-1] When R ₁ to R ₄ are hydrogen,

[Chemical Formula 4-2] When R ₂ to R ₄ are hydrogen and R ₁ is a phenyl group,

[Chemical Formula 4-3] When R _{3 and} R ₄ are hydrogen and R _{1 and} R ₂ are a phenyl group,

[Chemical Formula 4-4] When R _{3 and} R ₄ are hydrogen and R _{1 and} R ₂ are pyridyl groups,

[Chemical Formula 4-5] When R _{1 and} R ₄ are hydrogen and R _{2 and} R ₃ are a phenyl group,

[Chemical Formula 4-6] When R ₁ to R ₄ are a phenyl group,

In the above Chemical Formula 4-1 to Chemical Formula 4-6, L ₁ is an integer of 0 to 2. Ar ₁ is an aryl group having 6 to 30 carbon atoms (arylene group when L ₁ >0, but does not include a benzo compound), and Ar ₂ is an aralkyl group having 7 to 50 carbon atoms and 7 to 7 carbon atoms. a aralkyloxy group of 50, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, a heterocyclic ring having 5 to 50 carbon atoms, or a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms; Aromatic amines.

In order to more specifically describe the biscarbazole derivatives described in the present invention, the specific expression form is at least

Selected from the following groups, respectively

One of 138 new compounds is formed with the above Chemical Formulas 4-1 to 4-6, that is, the compounds of the compounds E to J in the specification examples. Compounds E to J are specific structural forms of the compound, but the series of compounds are not limited to the chemical structures listed. Any combination of R ₁ to R ₄ , Ar ₁ , Ar ₂ , and L ₁ within the above protective range should be included in the chemical formula 1.

Another aspect of the present invention is to provide a manufactured organic electric battery comprising the novel aromatic amine derivative of the above Chemical Formula 1. Photoluminescent device.

A further aspect of the invention is an organic light emitting device comprising a first electrode, a second electrode, and one or more organic compound layers interposed between the two electrodes, wherein at least one organic compound layer comprises at least one A novel aromatic amine compound of the invention.

The above novel aromatic amine derivative is a single form or a mixture with other substances including the above organic layer.

The organic layer includes at least a hole injection layer, a hole transport layer, a hole injection layer, a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injecting layer, and It has electronic transmission and any layer in the electron injection skill layer.

The hole injection layer, the hole transport layer, and at least one of the hole transporting layer including the hole injection are conventional hole injecting materials, hole transporting materials, and having both hole injecting and cavities. The transmission of skilled substances may also be substances produced by electron-transporting substances.

The term "organic layer" in this patent refers to the term of all layers disposed between the first electrode and the second electrode of the organic electronic device.

For example, the organic layer includes a light-emitting layer, and the organic layer includes one or more of a phosphorescent host, a fluorescent host, phosphorescent doping, and fluorescent doping, including the neo-aromatic amine derivative in the above-mentioned light-emitting layer, i) the fluorescent main body The above-mentioned neoaromatic amine derivative ii) may be the above-mentioned aromatic amine derivative iii), and the fluorescent main component and the fluorescent doping may be the above-mentioned neo-aromatic amine derivative.

The above-mentioned light-emitting layer may be a red, yellow or cyan light-emitting layer. For example, when the above-mentioned light-emitting layer is cyan, the above novel aromatic amine derivative is used in a cyan main body or a cyan doping application, and provides an organic light-emitting device having high efficiency, high brightness, high resolution, and long life.

Further, the organic layer includes an electron transport layer, and the electron transport layer includes the above novel aromatic amine derivative. Wherein the electron transporting layer further comprises a metal-containing compound in addition to the novel aromatic amine derivative.

Each of the organic layers includes a light-emitting layer and an electron transport layer, and each of the light-emitting layer and the electron transport layer includes the aromatic amine derivative (the light-emitting layer and the electron transport layer may be the same as or different from the new amine derivative) .

The above organic electronic device is prepared by using the novel aromatic amine derivative of the chemical formula 1 together with a conventional material and a method of preparing an organic electronic device.

Another aspect of the present invention is that the above device can be used in an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoconductor (OPC), or an organic thin film transistor (OTFT). The organic light-emitting device is formed by vapor deposition, electron beam evaporation, physical vapor deposition or the like on a substrate by vapor deposition of a metal and a conductive oxide and an alloy thereof to form an anode, the hole injection layer, the hole transport layer, and the light emission. The layer, the hole blocking layer and the electron transport layer are prepared by the above method of vapor-depositing the cathode. In addition to the above method, the organic material layer and the anode material of the cathode material on the substrate are sequentially vapor-deposited to form an organic light-emitting device.

The organic layer is a multilayer structure including a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer, and the organic layer is a solvent-engineered alternative vapor deposition method using various polymer materials. , for example, spin-coating, thin strip

Methods such as tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal imaging (Thermal-Imaging) reduce layer manufacturing.

The organic device according to the invention may also be illuminated front side, back side or double side depending on the material used.

The compound of the present invention is applicable to an organic light-emitting device, such as an organic solar cell, an OLED for illumination, a flexible OLED, an organic photoreceptor, or an organic transistor.

Another aspect of the present invention provides a process for producing the above novel aromatic amine derivative, which comprises a substitution reaction, a reduction reaction, a coupling reaction, an amination reaction and the like.

The preparation method of the above novel aromatic amine derivative is as follows:

Carry out a coupling reaction or an amination reaction stage according to the reaction formulas (1-1) and (1-2);

The stage of synthesizing Q-1 by subjecting the carbazole derivative to amination reaction according to the reaction formula (1-3);

According to the reaction formula (1-4), Q-1 is hydrolyzed to obtain a Q-2 method, and the intermediate of the reaction formula (1-1) and Q-2 are subjected to a reduction reaction to form a new aromatic amine compound.

on

In the chemical formula, the definitions of Ar ₁ and Ar ₂ and L ₁ and R ₁ to R ₄ are the same as those in the above Chemical Formula 1.

Beneficial effects:

The novel aromatic amine derivative of the present invention is a biscarbazole benzene in which the electron concentration of Ar ₁ and Ar ₂ is linked by an ether bond, and the related properties are improved, and the molecular weight of the R ₁ to R ₄ ligand of the biscarbazole is adjusted. The ligand type improves the performance and improves the function. The organic device using an amine derivative in the present invention has high luminance, excellent heat resistance, long life, and high efficiency.

detailed description

In the above chemical formula, the definitions of Ar ₁ and Ar ₂ and L ₁ and R ₁ to R ₄ are the same as those in the above Chemical Formula 1.

Specific includes:

A) coupling a compound of formula (a) with a compound of formula (b) to give a compound of formula (c);

B) coupling a compound of the formula (d) with a compound of the formula (e) to obtain a compound of the formula (f); then subjecting the compound of the formula (f) to the amination of the compound of the formula (g) to give a formula (Q-1) Compound;

C) hydrolyzing a compound of the formula (Q-1), followed by a coupling reaction with a compound of the formula (c) or a compound of the formula (h) to obtain a compound of the formula (1);

Steps A), B) have no precedence;

Where Y' is Br or I;

Y ₁ is Br, Cl or I;

L ₂ is an integer of 0 to 2 and is not 0;

Y ₂ and Y _{3 are} independently selected from -B(OH) ₂ or -NH ₂ ;

X ₁ , X _{2 are} independently selected from Br or I;

X ₃ , X _{4 are} independently selected from Cl, Br or I;

L ₁ is an integer of 0 to 2, when L ₁ is 0, Ar ₁ is an aryl group having 6 to 30 carbon atoms; when L ₁ > 0, Ar ₁ is an arylene group, and the Ar ₁ does not include benzo Class group

Ar ₂ is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a carbon number. a heterocyclic ring of 5 to 50, a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

R ₁ to R ₄ and R′ are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substitution or Unsubstituted aralkyl fluorenyl group having 7 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, and substituted or unsubstituted carbon atom number 6 to 30 Aromatic amines.

The above compound when R ₁ to R ₄ are both H is a compound of the formula (d) which is directly reacted with the compound of the formula (g) to obtain a compound of the formula (Q-1), and then the reaction of the step C) is continued. In this case, in the formula (d), X ₁ and X ₂ are both H.

In the present invention, the benzo group refers to a group in which a benzoheterocyclic compound loses two hydrogen atoms.

The following are examples of the invention, which are provided to assist the understanding of the invention, and are not intended to limit the scope of the invention. Further, the method for preparing a compound which is not specifically enumerated in each of the examples of the present invention is a method generally applied in the industry, and the method described in the examples can also be referred to when preparing other compounds.

Synthesis of the intermediate 9-(3-chloro-5-methoxyphenyl)-9H-carbazole (A-1):

1-bromo-3-chloro-5-methoxybenzene (10 mmol, 2.2 g), carbazole (20 mmol, 3.34 g)

A 100 mL three-necked flask was added, and cuprous iodide (2 mmol, 0.4 g), potassium carbonate (20 mmol, 1.4 g), o-phenanthroline (2 mmol, 0.4 g), DMF 50 mL, and reacted at 155 ° C for 3 d. Post-treatment: extraction, the organic phase was evaporated to dryness and then evaporated to ethyl ether, and then recrystallized from ethyl acetate and petroleum ether to give A-1 (1.53 g, y=50%).

Synthesis of intermediates A-2 and A-3:

The compound of the following [Table 1] was obtained in the same molar amount ratio according to the above-mentioned preparation method of Intermediate A-1.

【Table 1】

Synthesis of the intermediate 9,9'-(5-chloro-1,3-phenylene)bis(9H-carbazole) (A-4):

1,3,5-Tribromobenzene (10 mmol, 3.2 g), carbazole (40 mmol, 6.7 g) was added to 100 mL

A three-necked flask was charged with cuprous iodide (4 mmol, 0.8 g), potassium carbonate (40 mmol, 2.8 g), phenanthroline (4 mmol, 0.8 g), DMF 50 mL, and reacted at 155 ° C for 3 d. Post-treatment: extraction, the organic phase was evaporated to dryness and then evaporated to ethyl ether, and then recrystallized from ethyl acetate and petroleum ether to afford product A-4 (3.4 g, y=70%).

Synthesis of intermediate A-5:

The compound of the following [Table 2] was obtained in the same molar ratio according to the above-mentioned preparation method of Intermediate A-4.

【Table 2】

Synthesis of intermediate 4,4'-(5-chloro-1,3-phenylene)dipyridine (A-6):

1,3-Dibromo-5-chlorobenzene (10 mmol, 2.70 g), 4-pyridineboronic acid (20 mmol, 2.46 g), toluene (30 mL), aqueous potassium carbonate (2N, 16 mL) was placed in a three-neck bottle, nitrogen After the replacement, tetrakistriphenylphosphine palladium (0.2 mmol, 0.21 g) was added under nitrogen atmosphere, and the reaction was carried out at 90 ° C overnight to give A-6 (1.73 g, y = 65%).

Synthesis of intermediate A-7:

The compound of the following [Table 3] was obtained in the same molar amount ratio according to the above-mentioned preparation method of Intermediate A-6.

【table 3】

Synthesis of the intermediate 9-(4-chlorophenyl)phenanthrene (B-1):

9-Bromophenanthrene (10 mmol, 1.93 g), 4-chlorobenzeneboronic acid (10 mmol, 1.56 g), tetratriphenylphosphine palladium (0.01 mmol, 0.1 g), sodium carbonate aqueous solution (2N, 30 mL) were charged in 100 ml of three In a flask, after adding 30 ml of toluene, a vacuum was applied - three times of nitrogen gas, and the temperature was raised to 70 ° C, and the reaction was continued overnight. The reaction solution was cooled to room temperature, and the toluene phase was separated. The mixture was washed with a silica gel funnel to give a product, which was evaporated to dryness, and ethyl ether was dissolved in petroleum ether to precipitate B-1 (3.6 g, y=50%).

Synthesis of intermediates B-2 to B-7:

The following compounds of [Table 4] were obtained in the same molar ratio according to the above preparation method of Intermediate B-1:

【Table 4】

Synthesis of the intermediate 9,9'-(5-methoxy-1,3-phenylene)bis(9H-indazole) (C-1):

3,5-Dibromoanisole (10 mmol, 2.7 g), carbazole (60 mmol, 10 g) was added to 100 mL

A three-necked flask was charged with cuprous iodide (6 mmol, 1.2 g), potassium carbonate (60 mmol, 8.3 g), phenanthroline (6 mmol, 1.2 g), DMF 50 mL, and reacted at 155 ° C for 3 d. Post-treatment: extraction, the organic phase was evaporated to dryness and then evaporated to ethyl ether, and then recrystallized from ethyl acetate and petroleum ether to give product C-1 (3.9 g, y=90%).

Synthesis of intermediates C-2 and C-3:

The compound of the following [Table 5] was obtained in the same molar ratio according to the above preparation method of Intermediate C-1.

【table 5】

Synthesis of the intermediate 9-(3-(9H-carbazol-9-yl)-5-methoxyphenyl)-3-phenyl-9H-indazole (C-4):

9-(3-Chloro-5-methoxyphenyl)-9H-carbazole (10 mmol, 3.08 g), 3-phenyl-9H-carbazole (30 mmol, 7.29 g) was added to a 100 mL three-necked flask and added under nitrogen. Cuprous iodide (3 mmol, 0.6 g), potassium carbonate (30 mmol, 4.15 g), phenanthroline (3 mmol, 0.6 g), DMF 50 mL, was reacted at 180 ° C for 3 d. Post-treatment: extraction, the organic phase was evaporated to dryness and then evaporated with ethyl ether, and then recrystallized from ethyl acetate and petroleum ether to afford product C-4 (3.08 g, y=60%).

Synthesis of intermediates C-5 and C-6:

The following compounds of [Table 6] were obtained in the same molar ratio according to the above preparation method of Intermediate C-4:

[Table 6]

Synthesis of intermediate 3,5-bis(9H-carbazol-9-yl)phenol (D-1):

C-1 (20 mmol, 8.77 g), 47% HBr (11 mL) and trioctylmethylammonium chloride (2 g) were heated at 105 ° C in the reaction flask, and the reaction was terminated after half TLC. The column was extracted with ethyl acetate and water to give D-1 (7.64 g, y=90%).

Synthesis of intermediates D-2 to D-6:

The compound of the following [Table 7] was obtained in the same molar ratio according to the above preparation method of Intermediate D-1.

[Table 7]

Synthesis example:

EXAMPLES (Synthesis of Compound E-1):

Add 3,5-bis(9H-carbazol-9-yl)benzene (4.25 g, 10 mmol) to a 100 mL three-necked flask and dissolve it in 50 ml of acetonitrile, followed by cesium carbonate (20 mmol, 6.5 g), copper (0.2 mmol, 12 mg), 1-bromonaphthalene (11 mmol, 2.27 g) was reacted at 80 ° C for 4 h under nitrogen. After the reaction was completed, the organic phase was purified by column chromatography to give the product E-1 (5.28 g, y=66%), MS/ FAB (M ⁺ ): 550.23.

Examples E-2 to E-22:

According to the preparation method of the above Example E-1, the compound of the following [Table 8] was obtained in the same molar amount ratio.

[Table 8]

Synthesis of Examples F-1 to F-22:

The compound of the following [Table 9] was obtained in the same molar amount ratio according to the preparation method of the above Example E-1.

[Table 9]

Synthesis of Examples G-1 to G-22:

According to the preparation method of the above Example E-1, the compound of the following [Table 10] was obtained in the same molar amount ratio.

[Table 10]

Synthesis of Examples H-1 to H-22:

The compound of the following [Table 11] was obtained in the same molar amount ratio according to the preparation method of the above Example E-1.

[Table 11]

Synthesis of Examples I-1 to I-22:

The compound of the following [Table 12] was obtained in the same molar amount ratio according to the preparation method of the above Example E-1.

[Table 12]

Synthesis of Examples J-1 to J-8 and J-12 to J-22:

[Table 12]

Device preparation example:

Will Fisher's coating thickness is

The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, washed sequentially with isopropanol, acetone, and methanol for 30 minutes, repeatedly washed twice with distilled water, ultrasonically washed for 10 minutes, dried, and transferred to a plasma cleaning. In the machine, the substrate was washed for 5 minutes and sent to a vapor deposition machine. Evaporation of the hole injection layer 2-TNATA on the prepared ITO transparent electrode

Hole transport layer a-NPD or Example E to Example for material evaporation

Hole blocking layer and hole transport layer

cathode

The above process organic evaporation rate is maintained

LiF is

Al is

The electron emission characteristics of the organic light-emitting device manufactured by the above method are shown in Table 13.

[Table 13]

From the results of the above Table 13, it can be seen that the luminous efficiency and life characteristics of the novel aromatic amine derivative of the present invention are remarkably improved. It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

The present invention is an organic light-emitting device using a novel aromatic amine derivative, and as a result of obtaining good luminous efficiency and longevity, the present invention is useful in the highly practical OLED industry. The organic light-emitting device of the present invention is suitable for use in a flat panel display, a planar light-emitting body, a surface-emitting OLED light-emitting body for illumination, a flexible light-emitting body, a copying machine, a printer, an LCD backlight, or a light source, a display panel, a logo, and the like.

Claims

An aromatic amine compound characterized in that the molecular formula of the aromatic amine compound is:

Wherein, L 1 is an integer of 0 to 2, and when L 1 is 0, Ar 1 is an aryl group having 6 to 30 carbon atoms; when L 1 > 0, Ar 1 is an arylene group, and the Ar 1 is not included Benzo group;

Ar 2 is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a carbon number. a heterocyclic ring of 5 to 50, a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

R 1 to R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted group. An aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms. amine.
The aromatic amine compound according to claim 1, which has a structure of any one of Chemical Formula 2-1 to Chemical Formula 2-5:

In Chemical Formula 2-1 to Chemical Formula 2-5, L 1 is an integer of 0 to 2, and when L 1 is 0, Ar 1 is an aryl group having 6 to 30 carbon atoms; and when L 1 > 0, Ar 1 is an arylene group. And the Ar 1 does not include a benzo group;

Ar 2 is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a carbon number. a heterocyclic ring of 5 to 50, a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

R 1 to R 4 are independently selected from substituted or unsubstituted aralkyl groups having 7 to 50 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 50 carbon atoms, and substituted or unsubstituted carbon atoms. 7 to 50 aralkyl fluorenyl group, 6 to 50 carbon atoms aryl group, substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, or substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
The aromatic amine compound according to claim 1, which has a structure of any one of Chemical Formula 3-1 to Chemical Formula 3-8:

Here, Ar 2 is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or carbon. a heterocyclic ring having 5 to 50 atoms, a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

L 1 is an integer of 0 to 2, and R 1 to R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 7 to 50 carbon atoms. Alkoxy group, substituted or unsubstituted aralkyl fluorenyl group having 7 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, substituted or unsubstituted An aromatic amine having 6 to 30 carbon atoms.
The aromatic amine compound according to any one of claims 1 to 3, wherein the R 1 to R 4 are independently selected from the group consisting of:

Any of them;

Wherein X and Y independently represent an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and a substitution. Or an unsubstituted aralkyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, or a substituted or unsubstituted A substituted heterocyclic group having 5 to 30 carbon atoms or a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
The aromatic amine compound according to claim 1, wherein the compound is any one of Chemical Formula 4-1 to Chemical Formula 4-6.

among them,
Is any of the following groups:
An organic electro-device comprising a first electrode, a second electrode, and one or more organic compound layers interposed between the first electrode and the second electrode, wherein at least one organic compound layer comprises at least one The aromatic amine compound according to any one of claims 1 to 5.
The organic electrodevice according to claim 6, wherein the organic compound layer comprises a hole injecting layer, a hole transporting layer, and a hole injecting skill layer and a hole transporting skill layer, an electron blocking layer, The light-emitting layer, the hole blocking layer, the electron injecting layer, and the electron injecting skill layer and the electron injecting skill layer.
The organic electrodevice according to claim 6, wherein the organic electroluminescent device is an organic light emitting device, an organic solar cell, an electronic paper, an organic photoreceptor or an organic thin film transistor.
The method for synthesizing the novel aromatic amine compound according to any one of claims 1 to 5, which comprises using a substitution reaction, a reduction reaction, a C-C coupling reaction, and an amination reaction.
The preparation method according to claim 9, comprising:

A) coupling a compound of formula (a) with a compound of formula (b) to give a compound of formula (c);

B) coupling a compound of formula (d) with a compound of formula (e) to give a compound of formula (f); (f) a compound is aminated with a compound of formula (g) to give a compound of formula (Q-1);

C) hydrolyzing a compound of the formula (Q-1), followed by a coupling reaction with a compound of the formula (c) or a compound of the formula (h) to obtain a compound of the formula (1);

Steps A), B) have no precedence;

Where Y' is Br or I;

Y 1 is Br, Cl or I;

L 2 is an integer of 0 to 2 and is not 0;

Y 2 and Y 3 are independently selected from -B(OH) 2 or -NH 2 ;

X 1 , X 2 are independently selected from Br or I;

X 3 , X 4 are independently selected from Cl, Br or I;

L 1 is an integer of 0 to 2, when L 1 is 0, Ar 1 is an aryl group having 6 to 30 carbon atoms; when L 1 > 0, Ar 1 is an arylene group, and the Ar 1 does not include benzo Class group

Ar 2 is an aralkyl group having 7 to 50 carbon atoms, an aralkyloxy group having 7 to 50 carbon atoms, an aralkyl fluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a carbon number. a heterocyclic ring of 5 to 50, a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms;

R 1 to R 4 and R′ are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms, a substitution or Unsubstituted aralkyl fluorenyl group having 7 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heterocyclic ring having 5 to 50 carbon atoms, and substituted or unsubstituted carbon atom number 6 to 30 Aromatic amines.