KR101380008B1 - New anthracene derivatives and organic electronic device using the same - Google Patents

Abstract

The present invention provides a novel anthracene derivative and an organic electronic device using the same. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

Anthracene derivative, organic electronic device, organic light emitting device, organic light emitting device material

Description

Novel anthracene derivatives and organic electronic devices using the same {NEW ANTHRACENE DERIVATIVES AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

The present invention relates to a novel anthracene derivative and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires the exchange of holes and / or electrons between the electrode and the organic semiconductor material. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Is an electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. These devices include an electron / hole injecting material, an electron / hole extracting material, Materials or luminescent materials. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. In this case, the organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the organic light emitting device described above, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been sufficiently achieved, and therefore, the development of new materials is still required.

We have found an anthracene derivative with a novel structure. In addition, it has been found that when the organic layer of the organic electronic device is formed using the novel anthracene derivative, effects such as an increase in efficiency of the device, a decrease in driving voltage, and an increase in stability may be exhibited.

Accordingly, an object of the present invention is to provide a novel anthracene derivative and an organic electronic device using the same.

The present invention provides novel anthracene derivatives.

In addition, the present invention is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer is a novel anthracene derivative It provides an organic electronic device comprising.

The novel anthracene compound according to the present invention may be used as an organic material layer material of organic electronic devices including organic light emitting devices by introducing various aryl groups, heteroaryl groups, arylamino groups, etc. into the anthracene compounds. The organic electronic device including the organic light emitting device using the anthracene compound according to the present invention as a material of the organic material layer has excellent characteristics in efficiency, driving voltage, lifespan, and the like.

The novel anthracene derivative according to the present invention includes a compound represented by the following formula (1).

In Formula 1,

Ar ₁ is halogen, C ₁ ~ C ₄₀ alkyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₅ ~ C ₄₀ heteroaryl group and C ₆ ~ C ₄₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₆ ~ C ₄₀ arylamino group; Halogen, C ₁ ~ C ₄₀ alkyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₅ ~ C ₄₀ heteroaryl group and C ₆ ~ a heteroaryl group substituted with one or more groups selected from the group consisting of C ₄₀ aryl group or unsubstituted C ₅ ~ C _40; And halogen, C ₁ to C ₄₀ alkyl group, C ₁ to C ₄₀ alkoxy group, C ₃ to C ₄₀ cycloalkyl group, C ₆ to C ₄₀ aryl group, C ₅ to C ₄₀ heteroaryl group and C ₆ - substituted with one or more groups selected from the group consisting of C ₄₀ arylamino group or is selected from the group consisting of an aryl group unsubstituted C ₆ ~ C _40.

Ar ₂ and Ar ₃ are hydrogen; Halogen, C ₁ ~ C ₄₀ alkyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₅ ~ C ₄₀ heteroaryl group and C ₆ ~ an aryl group of C more than one selected from the group consisting of an aryl amino group of the ₄₀ group a substituted or unsubstituted C ₆ ~ C _40; Halogen, C ₁ ~ C ₄₀ alkyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₅ ~ C ₄₀ heteroaryl group and C ₆ ~ a heteroaryl group substituted with one or more groups selected from the group consisting of C ₄₀ aryl group or unsubstituted C ₅ ~ C _40; And halogen, C ₁ to C ₄₀ alkyl group, C ₁ to C ₄₀ alkoxy group, C ₃ to C ₄₀ cycloalkyl group, C ₆ to C ₄₀ aryl group, C ₅ to C ₄₀ heteroaryl group and C ₆ C ₆ to C ₄₀ arylamino group unsubstituted or substituted with one or more groups selected from the group consisting of arylamino groups of C ₄₀ , wherein one of Ar ₂ and Ar ₃ is necessarily hydrogen and both may be hydrogen There is no.

R1 and R2 are hydrogen; Substituted or unsubstituted C _{One Through} C ₄₀ Alkyl group; Halogen, C ₁ ~ C ₄₀ alkyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₅ ~ C ₄₀ heteroaryl group and C ₆ ~ C ₄₀ aryl substituted by at least one group selected from the group consisting of amino group or is selected from the group consisting of unsubstituted C ₆ ~ C ₄₀ aryl group, R1 and R2 may form a ring in combination.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

The alkyl group includes, but is not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.

The alkoxy group includes, but is not limited to, methoxy, ethoxy, phenyloxy, cyclohexyloxy, naphthyloxy, isopropyloxy, diphenyloxy and the like.

The aryl group includes a phenyl group, naphthyl group, anthracenyl group, biphenyl group, pyrenyl group, perylene group, tetrahydronaphthyl, derivatives thereof, and the like, but is not limited thereto.

The heteroaryl group includes but is not limited to thienyl, pyridyl, furyl, and the like.

The cycloalkyl group includes a cyclohexyl group, a cyclopentyl group, and the like, but is not limited thereto.

The arylamino group is naphthylamino group, biphenylamino group, anthracenylamino group, 3-methyl-phenylamino group, 4-methyl-naphthylamino group, 2-methyl-biphenylamino group, 9-methyl-anthracenylamino group, diphenylamino group , Phenyl naphthyl amino group, ditolyl amino group, phenyl tolyl amino group, carbazole group, triphenyl amino group and the like, but are not limited thereto.

The halogen includes fluorine, chlorine, bromine and iodine.

The compound of Formula 1 includes a compound represented by the following Formula 2 to Formula 3.

In Chemical Formula 2 and Chemical Formula 3,

_{Ar 1, Ar 2, Ar 3} , R1 and R2 are the same and _{Ar 1, Ar 2, Ar 3} , R1 and R2 of the formula (I).

Preferred specific examples of the compound of Formula 1 include the following compounds, but are not limited thereto.

Hereinafter, a method for preparing the compound of Formula 1 will be described.

Anthracene derivatives of formula 1 according to the present invention can be prepared by the following two methods.

First, a 10-bromoanthracene compound having an aryl group, a heteroaryl group or an arylamino group at position 1 of the anthracene structure, and an aryl boronic acid, heteroaryl boronic acid, and an arylamine compound may be prepared by reacting a palladium catalyst. It is preferable to prepare an anthracene derivative of the formula (2).

Second, it can be prepared by reducing 1,4-anthraquinone or by substituting positions 1 and 4 of anthracene via a Diels-Alder reaction, which is an anthracene derivative of Formula 3 It is preferable to prepare.

In addition, the organic electronic device according to the present invention is an organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, one or more of the organic material layer It characterized in that it comprises a compound of the formula (1).

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic material layer is formed using the above-described compounds.

Hereinafter, the organic light emitting device will be described.

In one exemplary embodiment of the present invention, the organic light emitting device may have a structure including a first electrode, a second electrode, and an organic material layer disposed therebetween. The organic layer in the organic light emitting device of the present invention may have a single layer structure of one layer or a multilayer structure of two or more layers including a light emitting layer. When the organic material layer of the organic light emitting device of the present invention has a multi-layer structure, for example, it may have a structure in which a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and the like are stacked. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers. For example, the organic light emitting device of the present invention may have a structure as shown in FIG. In Fig. 1, reference numeral 1 denotes a substrate, 2 an anode, 3 a hole injection layer, 4 a hole transport layer, 5 a light emitting layer, 6 an electron transport layer, and 7 a cathode. An organic light emitting device having a structure as shown in FIG. 1 is generally referred to as an organic light emitting device having a forward structure, but the present invention is not limited thereto and includes an organic light emitting device having a reverse structure. That is, the organic light emitting device of the present invention may have a structure in which a substrate, a cathode, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode are sequentially stacked.

When the organic light emitting device according to the present invention has a multi-layered organic material layer, the compound of Formula 1 is a light emitting layer, a hole transport layer, a layer for simultaneously transporting holes and light emission, a layer for simultaneously emitting light and electron transport, electron transport layer, electron transport And / or injection layers and the like. In the present invention, the compound of Formula 1 is particularly preferably included in the electron transport and / or injection layer or the light emitting layer.

The organic light emitting device according to the present invention may be manufactured using a conventional method and material for manufacturing an organic light emitting device, except that the compound of Formula 1 is used in at least one layer of the organic material layer of the organic light emitting device. For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and a material which can be used as a cathode is deposited thereon. In addition to the above method, in order to fabricate an organic light emitting device having a reverse structure as described above, an organic light emitting device may be manufactured by sequentially depositing an anode material, an organic material layer, and an anode material on a substrate.

The organic material layer may be formed by using a variety of polymer materials in a smaller number of layers by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Can be manufactured.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention, whereby the scope of the invention is not limited.

Preparation Example 1 Synthesis of Chemical Formula 1-1

Production Example 1-1 Synthesis of Compound A

Dissolve 1-chloroanthraquinone (50 g, 206 mmol) and naphthalene-1-boronic acid (42.5 g, 247 mmol) in tetrahydrofuran (400 ml), add 2M aqueous potassium carbonate solution, and add tetrakis (triphenylphosph). Pin) palladium (2.4 g, 2.07 mmol) was added thereto, followed by heating with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound A (52.3 g, yield 76%; MS: [M + H] ⁺ = 335).

≪ Preparation Example 1-2 > Synthesis of Compound B

Compound A (50 g, 150 mmol), acetic acid (300 ml) and hydroiodic acid (150 ml) were mixed and heated with stirring for 24 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous magnesium sulfate, and then distilled under reduced pressure and recrystallized with tetrahydrofuran and ethanol to obtain Compound B (29.8 g, yield 65%; MS: [M + H] ⁺ = 305).

≪ Preparation Example 1-3 > Synthesis of Compound C

Compound B (25 g, 82 mmol) was dissolved in chloroform (200 ml), and N-bromosuccinimide (15 g, 84 mmol) was added thereto and stirred. After completion of the reaction, water was poured and the organic layer was separated and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and column purification with hexane gave Compound C (18.5 g, yield 59%; MS: [M + H] ⁺ = 384).

Preparation Example 1-4 Synthesis of Chemical Formula 1-1

Compound C (9 g, 23.5 mmol) and naphthalene-1-boronic acid (4.9 g, 28.5 mmol) were dissolved in tetrahydrofuran (100 ml), followed by the addition of 2M aqueous potassium carbonate solution and tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol) was added and then heated with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and recrystallization with tetrahydrofuran and ethanol yielded Chemical Formula 1-1 (6.8 g, yield 67%; MS: [M + H] ⁺ = 431).

Preparation Example 2 Synthesis of Chemical Formula 1-2

Preparation Example 2-1 Synthesis of Chemical Formula 1-2

Compound C (9 g, 23.5 mmol) and phenanthrene-9-boronic acid (6.3 g, 28.5 mmol) in Preparation Example 1-3 were dissolved in tetrahydrofuran (100 ml), followed by addition of 2M aqueous potassium carbonate solution and tetrakis (Triphenylphosphine) palladium (0.58 g, 0.5 mmol) was added thereto, followed by heating with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate, distilled under reduced pressure and recrystallized with tetrahydrofuran and ethanol to obtain the chemical formula 1-2 (7.9 g, yield 70%; MS: [M + H] ⁺ = 481). .

Preparation Example 3 Synthesis of Chemical Formula 1-16

Production Example 3-1 Synthesis of Compound A

Dissolve 1-chloroanthraquinone (50 g, 206 mmol) and phenanthrene-9-boronic acid (54.8 g, 247 mmol) in tetrahydrofuran (400 ml), add 2M aqueous potassium carbonate solution, and add tetrakis (triphenyl Phosphine) palladium (2.4 g, 2.07 mmol) was added thereto and then heated with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and recrystallized with tetrahydrofuran and ethanol to obtain Compound A (54 g, yield 68%; MS: [M + H] ⁺ = 385).

<Production example 3-2> Synthesis of compound B

Compound A (50 g, 130 mmol), acetic acid (300 ml) and hydroiodic acid (130 ml) were mixed and heated with stirring for 24 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous magnesium sulfate, and then distilled under reduced pressure and recrystallized with tetrahydrofuran and ethanol to obtain compound B (29.2 g, yield 63%; MS: [M + H] ⁺ = 355).

PREPARATION EXAMPLE 3-3 Synthesis of Compound C

Compound B (28 g, 79 mmol) was dissolved in chloroform (200 ml), and N-bromosuccinimide (14.2 g, 80 mmol) was added thereto and stirred. After completion of the reaction, water was poured and the organic layer was separated and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and column purification with hexane gave Compound C (20.6 g, yield 60%; MS: [M + H] ⁺ = 434).

Preparation Example 3-4 Synthesis of Chemical Formula 1-16

Compound C (12 g, 27.7 mmol) and naphthalene-1-boronic acid (5.7 g, 33.2 mmol) were dissolved in tetrahydrofuran (120 ml), followed by the addition of 2M potassium carbonate solution and tetrakis (triphenylphosphine) palladium (0.64 g, 0.55 mmol) was added and then heated with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and recrystallization with tetrahydrofuran and ethanol yielded Chemical Formula 1-16 (8.3 g, yield 62%; MS: [M + H] ⁺ = 481).

Preparation Example 4 Synthesis of Chemical Formula 1-18

Preparation Example 4-1 Synthesis of Chemical Formula 1-18

Compound C (12 g, 27.7 mmol) and phenanthrene-9-boronic acid (7.4 g, 33.3 mmol) of Preparation Example 3-3 were dissolved in tetrahydrofuran (120 ml), followed by addition of 2M aqueous potassium carbonate solution and tetrakis (Triphenylphosphine) palladium (0.64 g, 0.55 mmol) was added thereto, followed by heating with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and recrystallized with tetrahydrofuran and ethanol to obtain the formula 1-18 (8.9 g, yield 67%; MS: [M + H] ⁺ = 481). .

Preparation Example 5 Synthesis of Chemical Formula 1-31

Production Example 5-1 Synthesis of Compound A

1,4-anthracenedione (25 g, 120 mmol) was dissolved in dioxane (300 ml), 3 M aqueous sodium hyposulfite solution (400 ml) was added slowly, and the mixture was stirred at room temperature for 18 hours. After the reaction was completed, the mixture was cooled to 0 ° C. and filtered. The mixture was washed several times with water and dried to obtain Compound A (14.8 g, yield 59%; MS: [M + H] ⁺ = 211).

<Production example 5-2> Synthesis of compound B

Dichloromethane (150 ml) was added to Compound A (14 g, 66.6 mmol), and triethylamine (7.1 g, 70 mmol) and trifluoromethanesulfonic anhydride (1937 g, 70 mmol) were slowly added thereto and stirred. . After completion of the reaction, water and dichloromethane were added to separate the organic layer, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, tetrahydrofuran: hexane = 1: 15 was purified by column to obtain Compound B (21.5 g, yield 68%; MS: [M + H] ⁺ = 475).

Preparation Example 5-3 Synthesis of Chemical Formula 1-31

Compound B (10 g, 21 mmol) and naphthalene-1-boronic acid (4.3 g, 25.2 mmol) were dissolved in tetrahydrofuran (100 ml), followed by the addition of 2M aqueous potassium carbonate solution and tetrakis (triphenylphosphine) palladium (0.49 g, 0.42 mmol) was added and then heated with stirring for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and recrystallization with tetrahydrofuran and ethanol yielded Chemical Formula 1-31 (6.7 g, yield 74%; MS: [M + H] ⁺ = 431).

Preparation Example 6 Synthesis of Chemical Formula 1-33

Preparation Example 6-1 Synthesis of Chemical Formula 1-33

Compound B (10 g, 21 mmol) and phenanthrene-9-boronic acid (5.6 g, 25.2 mmol) of Preparation Example 5-2 were dissolved in tetrahydrofuran (120 ml), followed by addition of 2M aqueous potassium carbonate solution and tetrakis (Triphenylphosphine) palladium (0.49 g, 0.42 mmol) was added thereto, followed by heating with stirring for 18 hours. After the reaction was completed, the temperature was lowered to room temperature, and the produced solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate, distilled under reduced pressure and recrystallized with tetrahydrofuran and ethanol to obtain the compound of formula 1-33 (7.1 g, yield 64%; MS: [M + H] ⁺ = 531). .

<Experimental Example 1>

The glass substrate coated with ITO (indium tin oxide) film with a thickness of 1,500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol was carried out and dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer.

[LINE]

4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 kV) of the following formula, which is a material for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. Formed.

[NPB]

Subsequently, the compound of Formula 1-1 prepared in Preparation Example 1 was vacuum deposited to a thickness of 300 kPa on the hole transport layer to form a light emitting layer. 4% of the following compound N, N, N, N'-tetraphenyl-1,6-pyrenediamine (N, N, N, N'-tetraphenyl-1,6-pyrenediamine) was used as a blue light emitting dopant in the light emitting layer. It was.

Alq ₃ (aluminum tris (8-hydroxyquinoline)) having the following chemical formula was vacuum deposited on the light emitting layer to form an electron injection and transport layer.

[Alq ₃ ]

On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kPa in order to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, aluminum 2 Å / sec, the vacuum degree during deposition is 2 × 10 ⁻⁷ to 5 × 10 ⁻⁸ torr was maintained.

<Experimental Example 2>

The organic light emitting device was manufactured by the same method as Experimental Example 1, except that the compound of formula 1-2 prepared in Preparation Example 2 was used instead of the compound of formula 1-1 in Experimental Example 1.

<Experimental Example 3>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound of formula 1-16 prepared in Preparation Example 3 instead of the compound of Formula 1-1 in Experimental Example 1.

<Experimental Example 4>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound of formula 1-18 prepared in Preparation Example 4 instead of the compound of Formula 1-1 in Experimental Example 1.

<Experimental Example 5>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound of formula 1-31 prepared in Preparation Example 5 instead of the compound of formula 1-1 in Experimental Example 1.

<Experimental Example 6>

The organic light emitting device was manufactured by the same method as Experimental Example 1, except that the compound of formula 1-33 prepared in Preparation Example 6 was used instead of the compound of formula 1-1 in Experimental Example 1.

&Lt; Comparative Example 1 &

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound represented by the following general formula 1 in place of the compound of formula 1-1 in Experimental Example 1.

[Formula 1]

The anthracene derivative of the present invention prepared according to the above example was applied to the organic light emitting device according to the experimental example, and the results measured at 10 mA are shown in Table 1 below.

Experimental Example
(Doping) compound Voltage (V) Luminance (Cd / A) Efficiency (Lm / W) Quantum Efficiency (Q.E) CIE (x) CIE (y) Comparative Example 1 1 6.49 6.39 3.08 5.62 0.129 0.168 Experimental Example 1 (1-1) 6.51 6.47 3.16 5.82 0.128 0.165 Experimental Example 2 1-2 6.48 6.42 3.07 5.49 0.129 0.170 Experimental Example 3 Formula 1-16 6.70 6.88 3.36 5.81 0.128 0.164 Experimental Example 4 Formula 1-18 6.83 6.52 3.09 5.88 0.129 0.173 Experimental Example 5 Formula 1-31 6.75 6.69 3.11 5.74 0.128 0.167 Experimental Example 6 Formula 1-33 7.01 6.90 3.23 5.65 0.128 0.165

As can be seen in Table 1, in the organic light emitting device using the anthracene derivative according to the present invention, the organic light emitting device using the compound represented by the general formula 1 showed higher characteristics in brightness, power efficiency, quantum efficiency, excellent blue Indicated.

1 illustrates an example of an organic light emitting device according to the present invention.

DESCRIPTION OF THE REFERENCE NUMERALS

1 substrate 2 anode

3 hole injection layer 4 hole transport layer

5 light emitting layer 6 electron transport layer

7 cathode

Claims (10)

An anthracene derivative represented by the following Formula 1: [Chemical Formula 1]

In Formula 1, Ar ₁ is a naphthyl group or a phenanthryl group, One of Ar ₂ and Ar ₃ is hydrogen, the other is a naphthyl group or phenanthryl group, R1 and R2 are hydrogen. The anthracene derivative according to claim 1, wherein the compound represented by Formula 1 comprises a compound represented by Formula 2 or Formula 3 below: (2)

(3)

In Chemical Formula 2 and Chemical Formula 3, _{Ar 1, Ar 2, Ar 3} , R1 and R2 are the same and _{Ar 1, Ar 2, Ar 3} , R1 and R2 of formula (I). The method of claim 1, wherein the anthracene derivative represented by Formula 1 is represented by the formula 1-1 to 1-3, 1-10, 1-11, 1-16 to 1-18, 1-31 to 1-33 and 1- Anthracene derivatives represented by any one of 35:

An organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes the anthracene derivative of claim 1 Organic electronic devices. The organic electronic device of claim 4, wherein the organic electronic device is an organic light emitting device. The organic electronic device of claim 5, wherein the organic light emitting device is an organic light emitting device having a forward structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. The organic electronic device of claim 5, wherein the organic light emitting device is an organic light emitting device having a reverse structure in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. The organic electronic device of claim 5, wherein the organic material layer of the organic light emitting device includes a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer. The organic electronic device of claim 5, wherein the organic material layer of the organic light emitting device includes a light emitting layer, and the light emitting layer includes the anthracene derivative. The organic material layer of claim 5, wherein the organic material layer of the organic light emitting device includes an electron transport layer, an electron injection layer, or an electron transport and electron injection layer, and the electron transport layer, the electron injection layer, or the electron transport and electron injection layer is formed of the anthracene derivative. An organic electronic device comprising.

Images