KR101645949B1 - Electroluminescent device using the electroluminescent compounds - Google Patents

Abstract

An organic electroluminescent device in which an organic layer is interposed between a cathode and a cathode on a substrate, characterized in that the organic layer is a light emitting layer containing at least one host compound represented by the following formula (1) and at least one dopant compound represented by the following formula To an organic electroluminescent device.

[Chemical Formula 1]

[In the above formula (1), ring A is a fused aromatic ring in which two or more rings are fused, provided that ring A is not benzoanthracene or tetracene.]

(2)

[L is a substituted or unsubstituted anthracenylene, pyrenylene, chrysenenylene, stilbeneylene, (C2-C60) alkenylene or (C2-C60) alkynylene.

The organic electroluminescent device according to the present invention exhibits excellent luminous efficiency, good color purity, and excellent driving life.

Host, dopant, organic electroluminescent device

Description

[0001] The present invention relates to an organic electroluminescent device using electroluminescent compounds,

An organic electroluminescent device in which an organic layer is interposed between a cathode and a cathode on a substrate, characterized in that the organic layer is a light emitting layer containing at least one host compound represented by the following formula (1) and at least one dopant compound represented by the following formula To an organic electroluminescent device.

[Chemical Formula 1]

[In the above formula (1), ring A is a fused aromatic ring in which two or more rings are fused, provided that ring A is not benzoanthracene or tetracene.]

(2)

L is a substituted or unsubstituted anthracenylene, pyrenylene, crylenylene, stilbenylene, (C2-C60) alkenylene or (C2-C60) alkynylene.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display device having a wide viewing angle, excellent contrast and fast response speed. In 1987, Eastman Kodak Co., An organic EL device using an aromatic diamine and an aluminum complex having a low molecular weight as a material for forming a light emitting layer has been developed for the first time [Appl. Phys. Lett. 51, 913, 1987].

An organic EL device is a device that injects electric charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to form an electron and a hole. It is possible to form a device on a flexible transparent substrate such as a plastic substrate and to operate at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, It is relatively small and has an advantage of excellent color. In addition, organic EL devices are capable of displaying three colors of green, blue, and red, making them a next-generation rich color display device and attracting a great deal of interest from many people.

The most important factors for determining the performance such as luminous efficiency and lifetime in an organic EL device are a light emitting material. Some characteristics required for such a light emitting material include a large quantum yield of light emission in a solid state and a high mobility of electrons and holes And should not be easily decomposed during vacuum deposition, and a uniform thin film should be formed and stabilized.

The organic EL device usually comprises anode / HIL / HTL / EML / ETL / EIL / cathode, and blue, green and red organic electroluminescent devices can be implemented according to how the emitting layer (EML) is formed.

On the other hand, the conventional materials for the light emitting compound for realizing a green or blue organic electroluminescent device have a problem in that the lifetime and luminous efficiency are poor.

Accordingly, the present inventors have made efforts to solve the above-mentioned problems, and as a result, they have found that in order to realize an organic electroluminescent device with high color purity, high brightness and long life, an organic material layer including a luminescent layer made of a combination of specific compounds is provided between the anode and the cathode Thereby realizing an inserted organic electroluminescent device.

An object of the present invention is to provide an organic electroluminescent device in which an organic material layer is inserted between a cathode and a cathode on a substrate, wherein the organic material layer comprises an emitting layer containing at least one host compound and at least one dopant compound And is to provide an organic electroluminescent device having excellent light emitting efficiency, excellent color purity, low driving voltage and good driving life.

More particularly, the present invention relates to an organic electroluminescent device, wherein an organic material layer is interposed between an anode and a cathode on a substrate, wherein the organic material layer is represented by the following Chemical Formula 1 An organic electroluminescent device comprising at least one host compound and at least one dopant compound represented by the following general formula (2).

[Chemical Formula 1]

[In the formula (1), ring A is a fused aromatic ring fused with two or more rings, except when ring A is benzoanthracene or tetracene; R ₁ to R ₆ independently represent hydrogen, deuterium, (C1-C60) alkyl, (C1-C60) alkoxy, (C6-C60) aryl, (C3-C60) heteroaryl, halogen, cyano, (C2- each other C60) alkenyl or (C2-C60) alkynyl, or R ₁ to R ₆ are connected to adjacent (C3-C60) alkylene or (C3-C60) alkenylene with or without a fused ring To form a fused ring; The ring A fused aromatic ring, and R ₁ to R ₆ of the alkyl, alkoxy, aryl or heteroaryl, alkenyl, alkynyl, with or without a fused ring with the adjacent substituents (C3-C60) alkylene or ( (C3-C60) alkenylene is selected from the group consisting of hydrogen, deuterium, (C1-C60) alkyl, (C6-C60) aryl, (C5- C60) heteroaryl, halogen, C60) alkynyl or cyano, and the substituents further substituted on the fused ring formed by the ring A and R < ₁ > to R < _{6 &} gt ;, or an alkylene or alkenylene with or without a fused ring, (C6-C60) aryl, (C3-C60) heteroaryl, 5 to 6 membered heterocycloalkyl comprising one or more heteroatoms selected from N, O and S, (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, di (C1-C60) (C6-C60) alkynyl, cyano, mono or di (C1-C60) alkylamino, mono or di (C6-C60) bicycloalkyl, (C1-C60) alkylthio, (C6-C60) aryloxy, (C6-C60) arylthio, (C1-C60) alkoxycarbonyl, (C1-C60) alkylcarbonyl, (C6-C60) arylcarbonyl, (C6-C60) arylcarbonyloxy, (C6-C60) aryloxycarbonyloxy, carboxy, nitro or hydroxy may be further substituted with one or more substituents .]

(2)

L is a substituted or unsubstituted anthracenylene, pyrenylene, chrysenenylene, stilbenylene, (C2-C60) alkenylene or (C2-C60) alkynylene, (C1-C60) aryl (C1-C60) alkyl, (C1-C60) alkenyl, (C6-C60) alkyl, halo (C1-C60) alkyl, mono or di (C6-C60) arylamino, mono- or di ≪ / RTI >aryl;

또는

이며;Ar ₁ and Ar ₂ are, independently from each other, a chemical bond, phenylene, fluorenylene,

or

;

R ₄₁ To R ₄₄ are independently hydrogen, halogen, deuterium, (C1-C60) alkyl, (C6-C60) aryl, (C4-C60) heteroaryl, mono or di (C6-C60) arylamino, mono or di each other ( (C3-C60) cycloalkyl, (C2-C60) alkenyl, (C2-C60) alkylamino, N-substituted heterocycloalkyl C2-C60) alkynyl, or, R ₄₁ to R ₄₄ is coupled with or without a fused ring with an adjacent substituent via (C3-C60) alkylene or (C3-C60) alkenylene may form a fused ring ;

The alkyl, aryl, heteroaryl, arylamino, alkylamino, cycloalkyl and heterocycloalkyl, adamantyl, cycloalkyl, alkenyl, alkynyl or fused ring of R ₄₁ to R ₄₄ may be hydrogen, deuterium, halogen, (C6-C60) aryl, (C4-C60) heteroaryl, 5 or 6 membered heterocycloalkyl comprising at least one member selected from N, O and S, (C3-C60) cycloalkyl (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, (C7-C60) bicycloalkyl, (C2- (C6-C60) alkenyl, (C2-C60) alkynyl, (C1-C60) alkoxy, cyano, mono or di (C6-C60) arylcarbonyl, (C6-C60) arylcarbonyl, (C1-C60) alkoxycarbonyl, , (C6-C60) aryloxycarbonyl, (C1-C60) alkoxycarbonyloxy, (C1-C60) alkylcarbonyloxy, (C6-C60) aryloxycarbonyloxy, (C1-C60) alkylcarbonyloxy, (C6-C60) arylcarbonyloxy, carboxyl, nitro or hydroxy. have.]

The organic electroluminescent device according to the present invention exhibits an efficient energy transfer mechanism between the host and the dopant, and can reliably exhibit the high-efficiency light emission characteristic based on the improvement of the electron density distribution. In addition, it is possible to overcome the initial efficiency lowering characteristic and low lifetime characteristic of existing materials, and to secure high performance light emitting characteristic having high efficiency and long life in each color.

The compound represented by the general formula (1) contained as a host in the organic electroluminescent device of the present invention includes the compounds represented by the following general formulas (3) to (9).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Wherein R ₁ to R ₆ are the same as defined in formula (1);

R ₁₁ Through R ₃₅ independently represent hydrogen, deuterium, (C1-C60) alkyl, (C6-C60) aryl, (C5-C60) heteroaryl, halogen, cyano, (C3-C60) alkenyl or (C3-C60 to each other ) Alkynyl, or (C3-C60) alkylene or (C3-C60) alkenylene with or without adjacent fused rings, to form a fused ring,

The R ₁₁ A to R ₃₅ alkyl, aryl, heteroaryl, alkenyl, alkynyl, alicyclic ring to form a fused ring with an adjacent substituent, or a monocyclic or polycyclic aromatic ring is selected from hydrogen, deuterium, halogen, (C1-C60) alkyl, (C6-C60) aryl, (C3-C60) heteroaryl, 5 to 6 membered heterocycloalkyl comprising at least one member selected from N, O and S, (C3-C60) cycloalkyl, tri (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, (C7-C60) bicycloalkyl, (C2-C60) alkenyl, (C6-C60) alkynyl, cyano, mono or di (C1-C60) alkylamino, mono- or di (C6-C60) arylthio, (C1-C60) alkoxycarbonyl, (C1-C60) alkylcarbonyl, (C6-C60) alkylthio, (C6-C60) arylcarbonyloxy, (C6-C60) aryloxycarbonyl, (C1-C60) alkoxycarbonyloxy, (C6-C60) aryloxycarbonyloxy, carboxyl, nitro, or hydroxy may be further substituted with one or more substituents selected from the group consisting of:

Alkyl " as used in the present invention includes a linear or branched saturated monovalent hydrocarbon radical consisting solely of a carbon atom and a hydrogen atom, or a combination thereof, and the term "alkyloxy" or "alkylthio" -Alkyl group or -S-alkyl group, wherein alkyl is as defined above.

&Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, . Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl, But is not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl includes 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl.

&Quot; Heteroaryl " in the present invention means an aryl group having 1 to 4 hetero atoms selected from N, O, S, P and Si as an aromatic ring skeletal atom and the remaining aromatic ring skeletal atom carbon, 5- to 6-membered monocyclic heteroaryl, and polycyclic heteroaryl which is condensed with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, Benzyloxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, and the like, but are not limited thereto .

The substituents containing the "(C1-C60) alkyl" moiety described in the present invention may have 1 to 60 carbon atoms, may have 1 to 20 carbon atoms, may have 1 to 10 carbon atoms It is possible. The substituents containing the "(C6-C60) aryl" moiety may have 6 to 60 carbon atoms, may have 6 to 20 carbon atoms, and may have 6 to 12 carbon atoms. The substituents containing the "(C3-C60) heteroaryl" moiety may have from 3 to 60 carbon atoms, may have from 4 to 20 carbon atoms, and may have from 4 to 12 carbon atoms. The substituents containing the "(C3-C60) cycloalkyl" moiety may have 3 to 60 carbon atoms, 3 to 20 carbon atoms, and may have 3 to 7 carbon atoms. The substituents containing the "(C2-C60) alkenyl or alkynyl" moiety may have 2 to 60 carbon atoms, may have 2 to 20 carbon atoms, and may have 2 to 10 carbon atoms.

The host compound of Formula 1 may be exemplified by the following compounds, but is not limited thereto.

The dopant compound of formula (2) may be specifically exemplified by the following compounds, but is not limited thereto.

The light emitting layer may be a single layer as a light emitting layer, or may be a plurality of layers in which two or more layers are stacked. In the case of using the dopant host in the constitution of the present invention in combination, it was confirmed that the luminous efficiency was remarkably improved.

In the organic electroluminescent device of the present invention, in addition to the electroluminescent compounds of the above formulas (1) and (2), an organic electroluminescent compound comprising an organic metal of group 1, group 2, group 4, periodic transition metal, lanthanide series and d- , And the organic layer may include a light emitting layer and a charge generating layer at the same time.

In addition, an organic electroluminescent device that emits white light by simultaneously including at least one organic light emitting layer emitting blue, green, and red light in addition to the organic light emitting compounds represented by the general formulas (1) and (2) may be formed in the organic material layer. The compounds emitting blue, green or red light are exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained.

Examples of the chalcogenide include SiO _x (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON and SiAlON. Examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , Rare-earth metals and the like. Preferable examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

In addition, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transport compound and the oxidative dopant is disposed on at least one surface of the pair of electrodes thus fabricated desirable. In this way, since the electron transfer compound is reduced to the anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof.

Also, a white organic light emitting device having two or more light emitting layers can be manufactured using a reducing dopant layer as a charge generating layer.

The organic electroluminescent device according to the present invention exhibits excellent luminous efficiency, good color purity, and excellent driving life.

Hereinafter, the luminescent characteristics of the device according to the present invention will be described in detail for the sake of a detailed understanding of the present invention, but the present invention is not limited thereto.

[Manufacturing Example]

[Preparation Example 1] Preparation of Compound 46

compound 1-1 Manufacturing

70 mL of dichloromethane and 15.8 g (118.8 mmol) of aluminum chloride were added to a round bottom flask and 8.0 g (54.0 mmol) of isobenzofuran-1,3- , 8.8 ml (64.8 mol) of 2,3,4-tetrahydronaphthalene was dissolved in 800 ml of dichloromethane and slowly added to a flask containing aluminum chloride. After stirring at 25 ° C for 24 hours, the reaction mixture was slowly added to 150 ml of 30 ml ice water containing 35% hydrochloric acid and stirred for an additional 20 minutes. The reaction mixture was extracted with 200 ml of ethyl acetate, recrystallized and dried to obtain Compound 1-1 (10.6 g, 37.8 mmol).

compound 1-2 Manufacturing

10.6 g (37.8 mmol) of Compound 1-1 , 50.4 g (378.1 mmol) of aluminum chloride and 11.1 g (189.0 mmol) of sodium chloride were added and the mixture was stirred under reflux at 130 ° C for 4 hours. The temperature of the reaction mixture was lowered to 25 DEG C, and 60 mL of tetrahydrofuran was added thereto to dissolve the reaction. 30 mL of water was added to terminate the reaction. After completion of the reaction, the reaction mixture was extracted with 100 mL of dichloromethane and dried under reduced pressure to obtain 3 g (11.4 mmol) of the compound 1-2 .

compound 1-3 Manufacturing

8.5 g (40.9 mmol) of 2-bromo naphthalene was dissolved in 50 mL of tetrahydrofuran. To 50 mL of the tetrahydrofuran dissolved in 2-bromonaphthalene was added n-butyllithium, 4.3 mL (45.7 mmol) of 2.5 M solution in n-hexane was added slowly at -72 캜, and after stirring for 2 hours, 3.0 g (11.4 mmol) of Compound 1-2 was added, and the mixture was stirred at room temperature for 24 hours. 50 mL of distilled water was slowly added to terminate the reaction. The reaction mixture was extracted with 250 mL of tetrahydrofuran and dried under reduced pressure to obtain 3.5 g (6.8 mmol) of the compound 1-3 .

compound 46 Manufacturing

4.5 g (27.1 mmol) of potassium iodide and 5.8 g (54.6 mmol) of sodiumhydrophosphinate were dissolved in 30 mL of acetic acid, 3.6 g (6.8 mmol) of Compound 1-3 , Dichloromethane in 10 mL of a mixed solution, and the mixture was stirred under reflux for 24 hours. Cooling to 25 ℃ was added 20 mL of water slowly to terminate the reaction, and then after the recrystallization was extracted with dichloromethane, 200 mL to give a dried compound 46 2.8 g (5.8 mmol, overall yield: 11%).

[Preparation Example 2] Preparation of Compound 12

compound 2-1 Manufacturing

20.9 g (102.9 mmol) of 9,9-dimethylfluorene and 27.5 g (205.9 mmol) of AlCl ₃ were dissolved in 500 mL of dichloromethane and then 22.9 g (154.4 mmol) of isobenzofuran- Lt; / RTI > After 12 hours, distilled water was added and the reaction was terminated. Then, 1 M HCl aqueous solution was added and extracted with MC. After distillation under reduced pressure, column separation was conducted to obtain Compound 2-1 (33.0 g, 96.4 mmol).

compound 2-2 Manufacturing

33.0 g (96.4 mmol) of the compound 2-1 was dissolved in 100 mL of sulfuric acid and 100 mL of acetic acid, and the mixture was stirred at 120 ° C. After 10 hours, the reaction mixture was cooled to room temperature, and distilled water was added to the reaction mixture to produce a solid. The resulting solid was filtered under reduced pressure and recrystallized from methanol and ethyl acetate to obtain 9.4 g (29.0 mmol) of the compound 2-2 .

compound 2-3 Manufacturing

15.0 g (72.5 mmol) of 2-bromonaphthalene was dissolved in 100 mL of THF, and 35 mL (87.0 mmol, 2.5 M in hexane) of n- BuLi was slowly added dropwise at -78 deg. After one hour, 9.4 g (29.0 mmol) of the compound 2-2 was added, followed by stirring at room temperature for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, dried over magnesium sulfate, and filtered under reduced pressure to obtain Compound 2-3 , which was used in the next step without purification.

compound 12 Manufacturing

Was dissolved the compound 2-3, KI 19.5 g (117.6 mmol ), NaH 2 PO 3 H 2 O 23.8 g (174.0 mmol) are not purified in 100 mL of acetic acid was stirred under reflux at 120 ℃. After 6 hours, the reaction mixture was cooled to room temperature, distilled water was added thereto, and the solid was filtered under reduced pressure. This was recrystallized from methanol, ethyl acetate and chloroform to obtain 6.6 g (12.1 mmol, 42%) of Compound 12 .

[Preparation Example 3] Preparation of Compound 23

compound 3-1 Manufacturing

20.0 g (102.9 mmol) of 9,9-dimethylfluorene and 27.5 g (205.9 mmol) of AlCl ₃ were dissolved in 500 mL of dichloromethane and then 35.0 g (154.4 mmol) of 5-bromoisobenzofuran- And the mixture was heated and stirred at 40 ° C. After 12 hours, distilled water was added and the reaction was terminated. Then, 1 M HCl aqueous solution was added and extracted with MC. After distillation under reduced pressure, column separation was carried out to obtain 40.6 g (96.4 mmol) of the compound 3-1 .

compound 3-2 Manufacturing

40.6 g (96.4 mmol) of the compound 3-1 was dissolved in 300 mL of sulfuric acid and 300 mL of acetic acid, and the mixture was stirred at 120 ° C. After 10 hours, the reaction mixture was cooled to room temperature, and distilled water was added to the reaction mixture to form a solid. The resulting solid was filtered under reduced pressure and recrystallized from methanol and ethyl acetate to obtain 11.6 g (29.0 mmol) of the compound 3-2 .

compound  3-3 Manufacturing

Compound 3-2 11.6 g (29.0 mmol), phenylboronic acid (Phenylboronic acid) 4.6 g (37.6 mmol), tetrakispalladium (0) triphenylphosphine _{(Pd (PPh 3) 4)} 1.7 g (1.6 mmol) of After dissolving in 250 mL of toluene and 80 mL of ethanol, 100 mL of a 2M sodium carbonate aqueous solution was added, and the mixture was refluxed and stirred at 120 ° C for 4 hours. Then, the temperature was lowered to 25 ° C, and distilled water was added to terminate the reaction. The reaction mixture was extracted with ethyl acetate and dried under reduced pressure. This was subjected to column chromatography to obtain 10.6 g (26.5 mmol) of the compound 3-3 .

compound 3-4 Manufacturing

15.0 g (72.5 mmol) of 2-bromonaphthalene was dissolved in 100 mL of THF, and 35 mL (87.0 mmol, 2.5 M in hexane) of n- BuLi was slowly added dropwise at -78 deg. After one hour, 10.6 g (26.5 mmol) of the compound 3-3 was added, followed by stirring at room temperature for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, dried over magnesium sulfate, and filtered under reduced pressure to obtain Compound 3-4 .

compound 23 Manufacturing

Was dissolved the compound 3-4, KI 19.5 g (117.6 mmol ), NaH 2 PO 3 H 2 O 23.8 g (174.0 mmol) are not purified in 100 mL of acetic acid was stirred under reflux at 120 ℃. After 6 hours, the reaction mixture was cooled to room temperature, distilled water was added thereto, and the solid was filtered under reduced pressure. This was separated into a column to obtain 4.2 g of compound 23 (6.1 mmol, 45%).

[Preparation Example 4] Preparation of Compound 27

compound 4-1 Manufacturing

20.0 g (73.2 mmol) of 2-bromo-9,9-dimethylfluorene and 19.5 g (146.4 mmol) of AlCl ₃ were dissolved in 500 mL of dichloromethane and then 22.9 g (154.4 mmol) of isobenzofuran- And the mixture was heated and stirred at 40 占 폚. After 12 hours, distilled water was added and the reaction was terminated. Then, 1 M HCl aqueous solution was added and extracted with MC. After distillation under reduced pressure, column separation was conducted to obtain 30.0 g (71.2 mmol) of the compound 4-1 .

compound 4-2 Manufacturing

30.0 g (71.2 mmol) of the compound 4-1 was dissolved in 100 mL of sulfuric acid and 100 mL of acetic acid, and the mixture was stirred at 120 ° C. After 10 hours, the reaction mixture was cooled to room temperature, and distilled water was added thereto. As a result, a solid was formed. The resulting solid was filtered under reduced pressure and recrystallized from methanol and ethyl acetate to obtain 4.0 g (9.9 mmol) of compound 4-2 .

compound 4-3 Manufacturing

4.0 g (9.9 mmol) of the compound 4-2 , 2.6 g (14.8 mmol) of phenylboronic acid, 10 mL of 3M K ₂ CO ₃ , 70 mL of toluene and 30 mL of ethanol were added and stirred under reflux. After 12 hours, the reaction mixture was cooled to room temperature, distilled water was added thereto, and the mixture was extracted with dichloromethane. This was dried with magnesium sulfate, filtered under reduced pressure, and separated into a column to obtain 3.5 g (8.7 mmo) of 4-3 .

compound 4-4 Manufacturing

3.4 g (21.8 mmol) of 4-bromobenzene was dissolved in 100 mL of THF, and 10.4 mL (26.1 mmol, 2.5 M in hexane) of n- BuLi was slowly added dropwise at -78 deg. After one hour, 3.5 g (8.7 mmo) of the compound 4-3 was added, followed by stirring at room temperature for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, dried over magnesium sulfate and filtered under reduced pressure to obtain the compound 4-4 .

compound 27 Manufacturing

Was dissolved the compound 4-4, KI 28.9 g (174.0 mmol ), NaH 2 PO 3 H 2 O 30.2 g (148.0 mmol) are not purified in 100 mL of acetic acid was stirred under reflux at 120 ℃. After 6 hours, the reaction mixture was cooled to room temperature, distilled water was added thereto, and the solid was filtered under reduced pressure. This was recrystallized from methanol, ethyl acetate and chloroform to obtain 3.5 g of compound 27 (6.7 mmol, 66%).

[Preparation Example 5] Preparation of Compound 28

compound 5-1 Manufacturing

14.1 mL (81.4 mmol) of 1-bromo-2-methylnaphthalene and 200 mL of pyridine are mixed, and 31.1 g of KMnO ₄ and 25 mL of distilled water are added at the same time. Add 10.0 g of KMnO ₄ and 30 mL of distilled water four times in total with refluxing stirring every 30 minutes. Add 200 mL of distilled water and stir at reflux for 12 hours. After hot filter, wash with boiling distilled water. The filtrate is concentrated under reduced pressure. Hydrochloric acid was added thereto, and the resulting solid was filtered under reduced pressure. And dried under reduced pressure to obtain 8.3 g (33.1 mmol) of the compound 5-1 .

compound 5-2 Manufacturing

8.3 g (33.1 mmol) of the compound 5-1 is dissolved in 100 mL of methanol, 2 mL of sulfuric acid is added, and the mixture is stirred. After 2 hours, add distilled water and extract with dichloromethane. Dried over magnesium sulfate and distilled under reduced pressure. The column was separated to obtain 6.8 g (25.7 mmol) of the compound 5-2 .

compound 5-3 Manufacturing

20.0 g (69.7 mmol) of 1-bromoanthracene-9,10-dione is dissolved in 200 mL of acetic acid, and 109.8 mL (819.7 mmol, 57%) of HI and 67.9 mL (655.7 mmol, 50%) of H ₃ PO ₂ are added. The mixture is refluxed for two days. Cool to room temperature, add distilled water, and filter the resulting solid under reduced pressure. Washed with KOH aqueous solution, and silica is filtered by dissolving the solid in chloroform. Recrystallization from ethyl acetate and methanol gave 14.0 g (54.8 mmol) of compound 5-3 .

compound 5-4 Manufacturing

Dissolve 14.0 g (54.8 mmol) of compound 5-3 in 500 mL of THF and slowly add 26 mL (65.4 mmol, 2.5 M in hexane) of n-BuLi at -78 ° C. After one hour, add 12.5 mL (112.0 mmol) of trimethyl borate. The temperature is slowly raised to room temperature and the mixture is stirred at room temperature for 12 hours. Add distilled water and extract with ethyl acetate. It is dried with magnesium sulfate and filtered under reduced pressure. The residue was distilled under reduced pressure and the residue was purified by column chromatography to obtain 8.0 g (36.0 mmol) of the compound 5-4 .

compound 5-5 Manufacturing

Compound 5-2 7.0 g (26.4 mmol), Compound 5-4 6.4 g (29.0 mmol), Pd (PPh 3) 4 1.2 g (1.1 mmol), Na 2 CO 3 8.3 g (79.2 mmol), 40mL of distilled water, toluene 100 mL of ethanol and 50 mL of ethanol were added, and the mixture was stirred under reflux for 5 hours. The reaction mixture was cooled to room temperature, distilled water was added thereto, and the mixture was extracted with ethyl acetate. Dried over magnesium sulfate and distilled under reduced pressure. Column separation afforded 8.2 g (22.6 mmol) of compound 5-5 .

compound 5-6 Manufacturing

8.0 g (22.1 mmol) of Compound 5-5 is dissolved in THF, and 25.7 mL (77.3 mmol, 3.0 M in diethyl ether) of methyl magnesium bromide is added. The mixture was heated and stirred at 60 占 폚. After 12 hours, cool to room temperature and add distilled water. Extracted with MC, dried over magnesium sulfate, and distilled under reduced pressure. The column was separated to obtain 7.0 g (19.3 mmol) of the compound 5-6 .

compound 5-7 Manufacturing

7.0 g (19.3 mmol) of Compound 5-6 is added to 100 mL of acetic acid and 100 mL of H ₃ PO ₄ is added. After heating at 100 ° C for 1 hour, cool to room temperature. Add distilled water and neutralize with aqueous NaOH solution. The mixture was extracted with MC and separated into a column to obtain 4.0 g (11.6 mmol) of the compound 5-7 .

compound 5-8 Manufacturing

4.0 g (11.6 mmol) of the compound 5-7 was dissolved in 100 mL of dichloromethane, and 5.2 g (29.0 mmol) of NBS was added. And the mixture was stirred at room temperature for 12 hours. The precipitate was distilled off under reduced pressure and the solid was washed with methanol, distilled water and hexane. 5.5 g (11.0 mmol) of the compound 5-8 was obtained.

compound 28 Manufacturing

Compound 5-8 5.5 g (11.0 mmol), phenyl boronic acid 5.6 g (32.9 mmol), Pd (PPh 3) 4 0.6 g (0.5 mmol), K 2 CO 3 4.5 g (32.9 mmol), distilled water 10 mL, toluene 50 mL of ethanol and 25 mL of ethanol, and the mixture was stirred under reflux for 5 hours. The mixture was cooled to room temperature and methanol was added thereto. The resulting solid was filtered under reduced pressure and washed sequentially with distilled water, methanol and hexane. EA, DMF / EA and THF / EA to obtain 5.2 g of compound 28 (8.7 mmol, 87%).

[Preparation Example 6] Preparation of Compound 36

compound 6-1 Manufacturing

1.7 g (70.1 mmol) of Mg turning was added to a 100 mL round bottom flask and a small amount of I 2 piece and 10 mL of tetrahydrofuran were added. 11 g (42.5 mmol) of 9-bromo-phenanthrene was dissolved in 10 mL of tetrahydrofuran and slowly added to a flask containing magnesium at 0 ° C., followed by stirring at 25 ° C. for 30 minutes. 9.9 g (43.4 mmol) of 5-bromo isobenzofurane-1,3-dione and 12.7 g (95.6 mmol) of aluminum chloride were added thereto, ≪ / RTI > The reaction solution was slowly added to 150 mL of 1N hydrochloric acid aqueous solution, stirred for 30 minutes, extracted with dichloromethane (200 mL), and dried under reduced pressure to obtain 11.4 g (28.2 mmol) of the compound 6-1 .

compound 6-2 Manufacturing

Compound 6-1 11.4 g (28.2 mmol) and aluminum chloride (Aluminum chloride) 37.9 g (284.4 mmol) and sodium chloride (sodium chloride) 8.3 g (142.2 mmol) of the method of Production Example 2 Compound 6-2 2.6 using g (6.8 mmol).

compound 6-3 Manufacturing

5.1 g (24.6 mmol) of 2-bromo naphthalene was dissolved in 100 mL of THF and 2.5 mL (27.3 mmol) of (n-butyllithium, 2.5M in n-hexane) was slowly added dropwise at -78 ° C. After one hour, 2.6 g (6.8 mmol) of the compound 6-2 was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, dried over magnesium sulfate and filtered under reduced pressure to obtain Compound 6-3 , which was directly used in the next reaction without purification.

compound 6-4 Manufacturing

2.5 g (14.8 mmol) and 3.1 g (29.6 mmol) of Compound 6-3 which had not been purified were dissolved in 100 mL of acetic acid, and the mixture was stirred under reflux at 120 ° C. After 6 hours, the reaction mixture was cooled to room temperature, distilled water was added thereto, and the solid was filtered under reduced pressure. This was separated into a column to obtain Compound ( 6-4 ) (1.95 g, 3.2 mmol).

compound 36 Manufacturing

Compound 6-4 1.95 g (3.2 mmol) and naphthalene boronic acid (naphthalene boronic acid) 664.0mg (3.9 mmol), palladium tetrakis triphenylphosphine _{(Pd (Ph 3) 4)} 0.2 g (1.7 mmol), 2M sodium carbonate 2.3 mL of the aqueous solution, 30 mL of toluene and 15 mL of ethanol was added, and the mixture was refluxed with stirring for 5 hours. When the reaction was complete, it was cooled to room temperature and methanol was added to generate a solid. The resulting solid was filtered under reduced pressure and washed sequentially with distilled water, methanol and hexane. EA, DMF / EA and THF / EA to obtain 1.2 g (2.2 mmol) of the compound 36 .

Organic luminescent compounds 1 to 49 were prepared using the methods of Preparation Examples 1 to 6, and ¹ H NMR and MS / FAB of the organic luminescent compounds prepared in Table 1 were shown.

[Table 1]

[Example 1] Fabrication of an OLED device using an organic light emitting compound according to the present invention

An OLED device having a structure using the light emitting material of the present invention was fabricated.

First, a transparent electrode ITO thin film (15 Ω / □) obtained from a glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially and stored in isopropanol Respectively.

Next, an ITO substrate was placed in a substrate folder of a vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine -TNATA) was added and the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. Then, a current was applied to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate.

The NPB -diphenyl-4,4'-diamine into the (NPB), by applying a current to the cell - Then, to another cell of the vacuum vapor-deposit device structure, N, N 'N, N -bis (α-naphthyl)' And evaporated to deposit a hole transport layer having a thickness of 20 nm on the hole injection layer.

A hole injecting layer and a hole transporting layer were formed, and then a light emitting layer was deposited thereon as follows. The compound 27 according to the present invention is added as a host to one cell in the vacuum vapor deposition apparatus and the compound F is added to the other cell as a dopant and the two substances are evaporated at different rates to 2 to 5 wt% Thereby depositing a light emitting layer having a thickness of 30 nm on the hole transporting layer.

Subsequently, tris (8-hydroxyquinoline) -aluminum (III) (Alq) having the following structure was deposited as an electron transfer layer to a thickness of 20 nm, and lithium quinolate (Liq) , And then an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition apparatus to fabricate an OLED.

Each compound was purified by vacuum sublimation under 10 ^-6 torr and used as an OLED light emitting material.

[Comparative Example 1] Production of an OLED device using a conventional light emitting material

After the hole injection layer and the hole transport layer were formed in the same manner as in Example 1, the DNA as the light emitting host material was placed in another cell in the vacuum vapor deposition apparatus, and the compound F was added to another cell, Evaporated at different rates and doped with 2 to 5 wt% based on the host to deposit a 30 nm thick emissive layer on the hole transport layer.

Subsequently, an electron transport layer and an electron injection layer were deposited in the same manner as in Example 1, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum vapor deposition apparatus to fabricate an OLED.

The luminescence efficiencies of the OLED devices each containing the organic luminescent compound according to the present invention and the conventional luminescent compound prepared in Example 1 and Comparative Example 1 were measured at 5,000 cd / m ² , respectively, and are shown in Table 2 below.

[Table 2]

As shown in Table 2, as a result of applying the material of the present invention to a green light emitting device, it was confirmed that the organic light emitting compound of the present invention maintained the color purity equal to or higher than that of Comparative Example 1, there was.

[Example 2] Fabrication of an OLED device using an organic light emitting compound according to the present invention

A hole injecting layer and a hole transporting layer were formed in the same manner as in Example 1, and then a light emitting layer was deposited thereon as follows. Compound 8 according to the present invention was added as a host to one cell in a vacuum evaporation apparatus and Compound A having the following structure was added as a dopant to another cell. Then, the two cells were heated to 2 to 5 wt% To deposit a 30 nm thick light emitting layer on the hole transporting layer.

Subsequently, an electron transport layer and an electron injection layer were deposited in the same manner as in Example 1, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum vapor deposition apparatus to fabricate an OLED.

[Comparative Example 2] Luminescence characteristics of OLED device using conventional light emitting material

After the hole injection layer and the hole transport layer were formed in the same manner as in Example 1, dinaphthylanthracene (DNA), which is a light emitting host material, was placed in another cell in the vacuum evaporation apparatus, and in another cell, Compound A was added thereto, and the two cells were heated together and evaporated to 2 to 5 wt% based on the host, thereby depositing a light emitting layer with a thickness of 30 nm on the hole transporting layer.

Subsequently, an electron transport layer and an electron injection layer were deposited in the same manner as in Example 1, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum vapor deposition apparatus to fabricate an OLED.

The luminous efficiencies of the organic light-emitting compounds prepared in Example 2 and Comparative Example 2 and the OLED devices containing the conventional light-emitting compounds were measured at 1,000 cd / m ² , respectively, and are shown in Table 3 below.

[Table 3]

As shown in Table 3, when the material of the present invention was applied to a blue light emitting device, it was confirmed that the light emitting efficiency was equal to or higher than that of Comparative Example 2.

Claims (5)

An organic electroluminescent device in which an organic material layer is interposed between a cathode and an anode on a substrate, wherein the organic material layer contains at least one host compound represented by the following Chemical Formulas 6, 8, or 9 and at least one dopant compound represented by Chemical Formula 2 An organic electroluminescent layer, and a light emitting layer. [Chemical Formula 6]

[Chemical Formula 8]

[Chemical Formula 9]

[In the formula 6, 8, and 9, R ₁ to R ₆ independently represent hydrogen, deuterium, (C1-C60) alkyl, (C1-C60) alkoxy, (C6-C60) aryl, (C3-C60) heteroaryl aryl, halogen, cyano, (C2-C60) alkenyl or (C2-C60) alkynyl, or, R ₁ to R ₆ is with or without a fused ring with the adjacent substituents (C3-C60) alkylene or (C3-C60) alkenylene to form a fused ring; R _15, R _16, R ₂₁ to R _28, and R ₃₂ to R ₃₅ independently represent hydrogen, deuterium, (C1-C60) alkyl, (C6-C60) aryl, (C5-C60) heteroaryl, halogen, (C3-C60) alkylene or (C3-C60) alkenylene which is unsubstituted or is substituted by a substituent which is adjacent to one another and which does not contain a fused ring, To form a fused ring, In the above-described R ₁ to R _6, alkyl, alkoxy, aryl or heteroaryl, alkenyl, alkynyl, with or without a fused ring with the adjacent substituents (C3-C60) alkylene or (C3-C60) alkenylene (C3-C60) alkynyl or cyano (C1-C60) alkoxy, wherein the fused ring may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, And the substituents further substituted in the fused ring formed by the alkylene or alkenylene linked with R &_lt; ₁ > to R &_lt; ₆ &_gt; or the adjacent substituent include hydrogen, deuterium, halogen, (C6-C60) aryl, (C3-C60) heteroaryl, 5 to 6 membered heterocycloalkyl comprising at least one member selected from N, O and S, (C3-C60) cycloalkyl, (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, (C7-C60) bicycloalkyl, (C6-C60) alkenyl, (C2-C60) alkynyl, cyano, mono or di (C1-C60) alkylamino, mono- or di (C1-C60) alkoxy, (C1-C60) alkylthio, (C6-C60) aryloxy, (C6-C60) arylcarbonyl, (C6-C60) arylcarbonyl, (C6-C60) aryloxycarbonyl, (C1- C60) alkoxycarbonyloxy, (C6-C60) aryloxycarbonyloxy, carboxyl, nitro, or hydroxy; An alicyclic ring which forms a fused ring with an adjacent alkyl, aryl, heteroaryl, alkenyl, alkynyl, adjacent substituent of R ₁₅ , R ₁₆ , R ₂₁ to R ₂₈ and R ₃₂ to R ₃₅ , The aromatic ring may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, (C1-C60) alkyl, (C6-C60) aryl, (C3-C60) heteroaryl, (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, (C7-C60) cycloalkyl, (C6-C60) alkenyl, (C2-C60) alkynyl, cyano, mono or di (C1-C60) alkylamino, mono or di (C1-C60) alkylthio, (C6-C60) arylthio, (C1-C60) alkoxy, (C1-C60) alkoxycarbonyloxy, (C1-C60) alkylcarbonyl, (C6-C60) arylcarbonyl, (C6-C60) arylcarbonyloxy, (C6-C60) aryloxycarbonyloxy, carboxyl, nitro or hydroxy may be further substituted with one or more substituents selected from the group consisting of hydrogen, alkylcarbonyloxy, ] (2)

[In the formula (2) L is substituted or unsubstituted anthracenylene, The substituted or unsubstituted anthracenylene of L may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 60) alkyl, (C 6 -C 60) C60) arylamino, mono or di (C1-C60) alkylarylamino, adamantyl, (C6-C60) aryl and (C3-C60) heteroaryl; Ar ₁ and Ar ₂ are, independently from each other, a chemical bond, phenylene, fluorenylene,

or

; R ₄₁ to R ₄₄ independently of one another are hydrogen, halogen, deuterium, (C 1 -C 60) alkyl, (C 6 -C 60) aryl, (C 4 -C 60) heteroaryl, mono or di (C3-C60) cycloalkyl, (C2-C60) alkylamino, N, O and S, , (C2-C60) alkynyl, or, R ₄₁ to R ₄₄ is coupled with or without a fused ring with an adjacent substituent via (C3-C60) alkylene or (C3-C60) alkenylene to form a fused ring Can be; The alkyl, aryl, heteroaryl, arylamino, alkylamino, cycloalkyl and heterocycloalkyl, adamantyl, cycloalkyl, alkenyl, alkynyl or fused ring of R ₄₁ to R ₄₄ may be hydrogen, deuterium, halogen, (C6-C60) aryl, (C4-C60) heteroaryl, 5 or 6 membered heterocycloalkyl comprising at least one member selected from N, O and S, (C3-C60) cycloalkyl (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, (C7-C60) bicycloalkyl, (C2- (C6-C60) alkenyl, (C2-C60) alkynyl, (C1-C60) alkoxy, cyano, mono or di (C6-C60) arylcarbonyl, (C6-C60) arylcarbonyl, (C1-C60) alkoxycarbonyl, (C6-C60) arylcarbonyloxy, (C6-C60) aryloxycarbonyl, (C1-C60) alkoxycarbonyloxy, (C6-C60) aryloxycarbonyloxy, (C1-C60) alkylcarbonyloxy, (C6-C60) arylcarbonyloxy, carboxyl, nitro or hydroxy. have.] delete The method according to claim 1, Wherein the organic layer further comprises at least one metal or complex compound selected from the group consisting of Group 1, Group 2, Group 4, Periodic transition metal, Lanthanide series metal and d-transition metal organic metal. Light emitting element. The method according to claim 1, Wherein the organic material layer comprises a light emitting layer and a charge generating layer. The method according to claim 1, Wherein at least one of the organic light emitting layers emitting blue, red, and green light is simultaneously included in the organic material layer to emit white light.