KR101146930B1 - Compound Containing At Least Two 5-Membered Heterocycle And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound comprising two or more five-membered hetero rings, an organic electric device using the same, and a terminal thereof.

Organic electric elements, heterocycles, five atoms

Description

Compound Containing At Least Two 5-Membered Heterocycle And Organic Electronic Element Using The Same, Terminal Thereof}

The present invention relates to a compound comprising two or more five-membered hetero rings, an organic electric device using the same, and a terminal thereof.

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 electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be classified. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. 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 above-described organic electroluminescent device, 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 electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

The present inventors have found a compound containing two or more five-membered heterocycles having a novel structure, and the application of the compound to organic electroluminescent devices can greatly improve the luminous efficiency, stability and lifetime of the device. Revealed.

Accordingly, an object of the present invention is to provide a novel compound comprising two or more five-membered heterocyclic rings, an organic electric device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula

The present invention provides hole injection materials, hole transport materials, light emitting materials and / or electron transport materials suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc., according to a compound comprising two or more five-membered heterocyclic rings. It is useful as a host material for phosphorescent dopants of various colors.

The present invention also provides an organic electric device using the compound having the above formula and a terminal including the organic electric device.

The compound of the present invention may play various roles in the organic electric device and the terminal, and when applied to the organic electric device and the terminal, it is possible to lower the driving voltage of the device, improve light efficiency and lifespan, and stability of the device.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

In the formula 1,

(1) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol Groups, substituted or unsubstituted C1-C50 alkyl groups, substituted or unsubstituted C1-C50 alkoxy groups, substituted or unsubstituted C1-C50 alkenyl groups, substituted or unsubstituted C5-C60 arylene groups , Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon ( At least one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or at least one containing sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or It is an unsubstituted heteroaryloxy group having 5 to 60 carbon atoms.

(2) R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R _8, and R ₉ and R ₁₀ combine with adjacent groups It can form a ring.

(3) X is sulfur (S), oxygen (O) or silicon (Si).

(4) Y represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 To 60 arylene group, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus ( A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one or at least one containing sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or an unsubstituted heteroaryloxy group having 5 to 60 carbon atoms.

(5) n is an integer of 1-3.

(6) The compound having the above structural formula can be used in a soluble process.

The present invention provides a compound of Formulas 2 to 9 below.

(7) R ₁₁ is a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or Substituted or unsubstituted C5 to 60 containing at least one or more unsubstituted aryl group having 5 to 60 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Is a heteroaryl group.

(8) Ar ₁ and Ar ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 to A substitution containing at least one arylene group of 60, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or It is an unsubstituted heteroaryl group having 5 to 60 carbon atoms.

(9) R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 to A substitution containing at least one arylene group of 60, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or It is an unsubstituted heteroaryl group having 5 to 60 carbon atoms.

(10) Z independently represents a single bond, or-O-,-S-,-CO-,-SO ₂ -,-NR ₁₄ -,-PR ₁₅ -,-SiR ₁₆ R _17- , substituted or unsubstituted A C1-C50 alkyl group of a ring, a substituted or unsubstituted C1-C50 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, a substituted or unsubstituted C5-C60 aryl group or sulfur (S), Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).

(11) R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, substituted or At least one of an unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) It is a substituted or unsubstituted C5-C60 heteroaryl group containing the above.

Specific examples of the compounds belonging to Formulas 2 to 5 which are compounds including two or more five-membered hetero rings according to one embodiment of the present invention include the compounds of Formula 6 below, but the present invention is not limited thereto.

Various organic electric devices exist in which compounds including two or more five-membered hetero rings described with reference to Chemical Formulas 1 to 6 are used as the organic material layer. Examples of the organic electroluminescent device in which compounds including two or more five-membered hetero rings described with reference to Chemical Formulas 1 to 6 may be used include, for example, an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, Organic transistors (organic TFTs), photodiodes, organic lasers, laser diodes, and the like.

One example of an organic electroluminescent device to which compounds including two or more five-membered hetero rings described with reference to Chemical Formulas 1 to 6 may be applied, but the present invention is not limited thereto. The compound including two or more five-membered hetero rings described above may be applied to the organic electric device.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formula 1 to 6 Provided is a light emitting device.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

The organic light emitting device according to another embodiment of the present invention, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer And a structure known in the art using conventional manufacturing methods and materials in the art, except that at least one layer of the organic material layer including the electron injection layer is formed to include the compounds of Formulas 1 to 6. It can be prepared as.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound including two or more five-membered heterocyclic rings described with reference to Chemical Formulas 1 to 6 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the compound including two or more five-membered heterocyclic rings described with reference to Chemical Formulas 1 to 6 includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and a protective layer. It may be used in place of one or more, or may be used in conjunction with them to form a layer. Of course, the organic layer may be used not only in one layer but also in two or more layers.

Particularly, hole injection materials, hole transport materials, and luminescence suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, and white, according to compounds including two or more five-membered hetero rings described with reference to Chemical Formulas 1 to 6 It is useful as a material and / or electron transport material, as a host material for phosphorescent dopants of various colors, and in particular as a phosphorescent host material in green.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials 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, Layer.

The organic light emitting device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer, by a soluble process of a compound including two or more five-membered hetero rings described above.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As a positive electrode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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 hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

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

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer positioned thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, a hole injection material, a hole transport material, suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, and white, according to a compound including two or more five-membered heterocycles described with reference to Chemical Formulas 1 to 6, It can be used as a light emitting material, an electron transporting material and an electron injection material, and can be used as a host material for phosphorescent dopants of various colors.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, various computers, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, the preparation or synthesis examples of the compound containing two or more five membered hetero rings belonging to the formula (6). However, since a large number of compounds including two or more five-membered heterocyclic rings belonging to Formula 6, one or two of the compounds including two or more five-membered hetero rings belonging to Formula 6 will be described. Those skilled in the art, that is, those skilled in the art can prepare a compound including two or more five-membered hetero rings belonging to the present invention, which are not illustrated by the preparation examples described below.

Step 1) Synthesis of Intermediate A

After 2-bromothioanisole was dissolved in glacial acetic acid solvent, the reaction temperature was lowered to 0 ° C., and hydrogen peroxide was slowly added dropwise. When the dropwise addition was completed, the temperature of the reaction product was raised to room temperature, followed by stirring for 12 hours. After the reaction was completed, the solvent was removed using a reduced pressure apparatus, extracted with CH ₂ Cl ₂ and washed with NaHCO ₃ aqueous solution. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated using column chromatography to give the desired intermediate A (yield: 98%).

Step 2) Synthesis of Intermediate B

The intermediate A, 2-bromocarbazole, Pd (PPh ₃ ) ₄ and Na ₂ CO ₃ obtained in step 1) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated using column chromatography to give the desired intermediate B (yield: 51%).

Step 3) Synthesis of Intermediate C

The intermediate B obtained in step 2) was dissolved in a trifluoromethanesulfonic acid solvent, and then stirred at room temperature for 48 hours. After the reaction was completed, the reaction was poured into a mixture of water and pyridine solvent and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate C (yield: 38%).

Synthesis Example 1 : Synthesis of Compound 4

Intermediate C, bromobiphenyl, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 3) were dissolved in a toluene solvent and stirred at 110 ° C. for 6 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 4 by column chromatography (yield: 77%).

Synthetic example  2: synthesis of compound 52

The intermediate C and 4,4'-dibromobiphenyl, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 3) were dissolved in a toluene solvent and stirred at 110 ° C. for 12 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the resulting compound 52 by column chromatography (yield: 62%).

Synthetic example  3: Synthesis of Compound 70

Compound 4, NBS ( N- bromosuccinimide) and BPO (benzoyl peroxide) obtained in Synthesis Example 1 were dissolved in CH ₂ Cl ₂ , and stirred at room temperature for 3 hours. Upon completion of the reaction, an aqueous sodium bicarbonate solution was added, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate D (yield: 80%). Thereafter, intermediate D and diphenylamine, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in a toluene solvent, and then stirred at 110 ° C. for 9 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the desired product 70 by column chromatography (yield: 60%).

Synthetic example  4: Synthesis of Compound 75

The intermediate D obtained in the above step was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n- BuLi (2.5 M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product obtained by concentration of the organic solvent was separated by column chromatography to give the desired intermediate E (yield: 66%).

Thereafter, intermediate E, intermediate D, diphenylamine, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in a toluene solvent, and then stirred at 110 ° C. for 6 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 75 by column chromatography (yield: 37%).

abandonment Field  Manufacturing evaluation of the device

Compounds 4 , 52 , 70 , and 75 obtained through synthesis were used as light emitting host materials of the light emitting layer, respectively, to fabricate an organic light emitting diode according to a conventional method. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as a-NPD) was vacuum-deposited on the membrane as a hole transport compound to a thickness of 30 nm. A hole transport layer was formed. After the hole transport layer was formed, each of compounds 4 , 52 , 70 or 75 was deposited as a phosphorescent host material on the hole transport layer to form a light emitting layer. At the same time, tris (2-phenylpyridine) iridium (abbreviated as I r (ppy) ₃ hereinafter) was added as a phosphorescent Ir metal complex dopant. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer to a thickness of 10 nm. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was formed into an electron injection layer to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

Comparative Experimental Example

For comparison, instead of the compound of the present invention, a compound represented by Chemical Formula 7 (hereinafter abbreviated as CBP) was used as a light emitting host material, thereby fabricating an organic EL device having the same structure as in the evaluation test for manufacturing an organic EL device.

Emitting layer
Host material Voltage
(V) Current density
(mA / cm ² ) Luminance
(cd / m ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 4 5.9 0.31 105 44.2 (0.30, 0.60) Example 2 Compound 52 5.8 0.33 112 49.2 (0.32, 0.61) Example 3 Compound 70 6.0 0.31 107 41.7 (0.30, 0.60) Example 4 Compound 75 5.8 0.32 110 48.3 (0.30, 0.60) Comparative Example 1 CBP 6.1 0.31 101 32.6 (0.33, 0.61)

As can be seen from the results of Table 1, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity but also green light emission of long life is obtained, green phosphorescent host material of the organic light emitting device It can be used to significantly improve the luminous efficiency and lifetime.

When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting layer, as well as an electron injection layer, an electron transport layer, a hole injection layer and a hole transport layer, it is obvious that the same effect can be obtained.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments.

The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

Claims (11)

A compound represented by the following formula.

In the above formulas, (1) R ₁ , R ₂ , and R ₄ to R ₁₀ are hydrogen atoms, (2) R ₃ is a hydrogen atom; Aryl groups having 6 to 30 carbon atoms; Heteroaryl group having 5 to 30 carbon atoms that is unsubstituted or substituted with a C ₆ -C ₃₀ aryl group and includes at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ; Or a fluorene group unsubstituted or substituted with a C ₁ -C ₆ alkyl group, (2) X is sulfur (S), (3) Y is an arylene group having 6 to 30 carbon atoms; Aryl groups having 6 to 30 carbon atoms; Heteroaryl group having 5 to 30 carbon atoms that is unsubstituted or substituted with a C ₆ -C ₃₀ aryl group and includes at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ; Or a fluorene group unsubstituted or substituted with a C ₁ -C ₆ alkyl group, (4) Said n is an integer of 1-3. delete delete Compound which is one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1 or claim 4. The method of claim 5, The organic electroluminescent device according to claim 1, wherein the organic layer is formed by a solution process. The method of claim 5, The organic electroluminescent device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially. The method of claim 7, wherein The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. The method of claim 7, wherein The organic material layer includes a light emitting layer, And the compound is used as the green phosphorescent host material in the light emitting layer. A display device comprising the organic electric element of claim 5; And a control unit for driving the display device. The method of claim 10, The organic electroluminescent device includes an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), a photodiode, an organic laser, and a laser diode. Terminal) characterized in that one of.

Images