KR20110100762A - Spirocabazole compund having spiro framework and organic electroric element using the same, terminal thererof - Google Patents

Abstract

The present invention provides a spiro carbazole compound including a spiro skeleton, an organic electronic device using the same, and a terminal thereof.

Description

Spyrocarbazole compound comprising a spiro skeleton and an organic electronic device using the same, and a terminal thereof TECHNICAL FIELD

The present invention relates to a spiro carbazole compound containing a spiro skeleton, an organic electronic 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 electronic device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, 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 to increase the efficiency and stability of the organic electronic device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

Materials used as the organic material layer in the organic electronic device 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 depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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 organic electronic 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 electronic device has not been sufficiently achieved, and therefore, the development of a new material is still required.

The present inventors have found a spiro carbazole compound containing a spiro skeleton, and the compound has excellent electrical and luminescent properties, so that when applied to organic electronic devices, it has excellent hole injection and hole transport ability under low driving voltage. It has been found to be useful as a hole injection material and a hole transporting material having.

Accordingly, an object of the present invention is to provide an aromatic amine compound having various substituents, an organic electronic device using the same, and a terminal thereof.

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

At this time, the compound according to an embodiment of the present invention provides a spiro carbazole compound including a spiro skeleton.

The present invention has an aromatic amine compound having a variety of substituents and organic electronic device using the same, it can play a variety of roles in the terminal, and when applied to the organic electronic device and the terminal has excellent electrical characteristics and light emission characteristics excellent hole under low driving voltage It is useful as a hole injection material and a hole transport material having injection and hole transport ability. The present invention is also useful as a host material for phosphorescent dopants of various colors, depending on the compound. In the case of employing the organic film using the organic electroluminescent compound described above, an organic electronic device having high efficiency, low voltage, high brightness, and long life based on superior current density characteristics can be manufactured.

1 to 5 show examples of organic electronic devices to which the compounds of the present invention can be applied.

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 describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. 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 should be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

In the above formula,

(1) R ₁ , R ₂ , R ₃ and R ₄ are each independently or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 60 carbon atoms, substituted or unsubstituted carbon atoms 1 to A 60 alkenyl group, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O) , A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and It is a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one silicon (Si).

(2) R _a , R _b , R _c and R _d are each independently of each other a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 Alkoxy group of 60 to 60, substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, substituted or unsubstituted arylene group of 5 to 60 carbon atoms, substituted or unsubstituted aryl group of 5 to 60 carbon atoms, substituted or unsubstituted carbon atoms 5 Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur containing at least one aryloxy group, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) of 60 to 60 A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one sulfur (S), nitrogen (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); N), a substituted or unsubstituted heteroatom having 1 to 60 carbon atoms containing at least one of oxygen (O), phosphorus (P) and silicon (Si) It is a ryloxy group.

(3) Ar ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), It is a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).

(3) n is an integer of 1-4.

(4) R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ may combine with an adjacent group to form a substituted or unsubstituted ring.

The compound described above may be represented by the following formula (2).

In the above formula,

Ar ₁ is as defined above, Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or Substituted or unsubstituted C1 to 50 containing at least one or more unsubstituted aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one alkyl group or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), Nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) is a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms.

In addition, the compound described above may be represented by the following formula (3).

In the above formula,

Ar ₁ is as defined above, and R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 to Alkoxy group of 60, substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted carbon atoms 5 to 60 A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur containing at least one aryloxy group of 60, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen (N ) Substituted or unsubstituted carbon number containing at least one, oxygen (O), phosphorus (P) and silicon (Si) 1 To heteroaryloxy group of 60.

In addition, the compound described above may be represented by the following formula (4).

In the above formula,

Ar ₁ is as defined above, R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted C 1 to 60 An alkoxy group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5-C60 A substituted or unsubstituted C1-C50 alkyl group or sulfur (S) containing at least one or more of an aryloxy group, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N) , Substituted or unsubstituted carbon atoms containing at least one, oxygen (O), phosphorus (P) and silicon (Si) 1 to 60 heteroaryloxy group.

As a result, the compounds according to the examples provide spiro carbazole compounds comprising a spiro backbone.

As a specific example of a compound according to an embodiment of the present invention, there are compounds of the formula (5) belonging to the formulas (1) to 4, but the present invention is not limited thereto.

Various organic electronic devices exist in which the compounds described with reference to Chemical Formulas 1 to 5 are used as hole injection materials and hole transport materials. Examples of the organic electronic device in which the compounds described with reference to Chemical Formulas 1 to 5 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), and a photodiode. It can be used in organic semiconductor materials such as photodiode, organic laser, laser diode.

As an example, among the organic electronic devices to which the compounds described with reference to Chemical Formulas 1 to 5 may be applied, organic light emitting diodes (OLEDs) will be described below. However, the present invention is not limited thereto and the compounds described above may be applied to various organic electronic devices. Can be.

Another embodiment of the present invention is an organic electronic device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one layer of the organic material layer comprises an organic electric field comprising the compounds of Formulas 1 to 5 Provided is a light emitting device.

An organic light emitting display device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer to form the compound of Formula 1 to 5 It can be prepared in a structure known in the art using conventional manufacturing methods and materials in the art. The structure of the organic light emitting display device according to the present invention is illustrated in FIGS. 1 to 5, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer, 104 a hole transport layer, 105 a light emitting layer, 106 an electron injection layer, and 107 a cathode.

Compounds described with reference to Formulas 1 to 5 may be included in one or more of a hole injection layer and a hole transport layer. Specifically, the compounds described with reference to Formulas 1 to 5 may be used in place of one or more of the hole injection material and hole transport material described below, or may be used by forming a layer with them. Of course, it is not only used in one layer of the organic material layer but may be used in two or more layers.

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

In addition to the above method, an organic electronic device may be manufactured 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, and an electron transport 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 the soluble process of the compounds 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 the anode material, a material having a large work function is usually 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 located 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 and silicon germanium oxide. Compounds, silicone arylamine compounds 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 A small amount of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) is used. When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

As described above, the compounds described with reference to Chemical Formulas 1 to 5 may form a corresponding layer instead of the hole injection layer and the hole transport layer or together with existing materials, or may be formed as host materials of phosphorescent dopants of various colors depending on the compound. You may.

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 cathode is positioned on the electron transport layer. This cathode serves to inject electrons into the electron transport layer. 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.

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 electronic device 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 control, 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 Production 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 for the compounds belonging to the formula (5). However, since the number of compounds belonging to Formula 5 is large, one or more of the compounds belonging to Formula 5 will be exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare the compounds belonging to the present invention not illustrated through the preparation examples described below.

Step 1) Synthesis of Intermediate A

 Scheme 6a

2-Bromo-9H-fluorene was dissolved in Pyridine solvent, Tetrabutylammonium hydroxide was slowly added dropwise in Methanol solvent and stirred at room temperature. After the reaction was completed, the mixture was extracted with Ethyl acetate. After removing a small amount of water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was recrystallized using Methanol to give the desired intermediate A (yield: 90%).

Step 2) Synthesis of Intermediate B

 Scheme 6b

2-Bromobiphenyl was dissolved in anhydrous THF solvent, the reaction temperature was lowered to 78 ° C., and t-Butyllithum was slowly added dropwise and stirred for 1 hour. The intermediate B synthesized in step 1) was dissolved in THF solvent and slowly added dropwise, followed by stirring for 12 hours. After completion of the reaction, the mixture was extracted with Ethyl acetate, a small amount of water in the reaction 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 obtain the desired intermediate B (yield). : 54%).

Step 3) Synthesis of Intermediate C

 Scheme 6c

 Intermediate C synthesized in step 2) was dissolved in acetic acid solvent, the temperature of the reactant was lowered to 0 ° C., and HCl was slowly added dropwise. After the reaction was completed, the resulting crystals were separated by filtration under reduced pressure to give the desired intermediate C (yield: 72%).

Step 4) Synthesis of Intermediate D

 Scheme 6d

The intermediate C synthesized in step 3) was dissolved in anhydrous THF, the reaction temperature was lowered to 78 ° C., n-BuLi (1.6 M in hexane) was slowly added dropwise, and the reaction was stirred for 30 minutes. The temperature of the reaction was lowered to 78 ° C. and Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise. At the end of the reaction, the mixture was extracted with Ethyl acetate, a small amount of water in the reaction was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. 71%).

Step 5) Synthesis of Intermediate E-1

 Scheme 6e

The intermediate D synthesized in step 4), 1-Bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ 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, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate E-1 (yield: 73%).

Step 6) Synthesis of Intermediate E-2

 Scheme 6f

The intermediate D and 2,5-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ synthesized in step 4) 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 obtain the desired intermediate E-2 (yield: 70%).

Step 7) Synthesis of Intermediate E-3

 [Scheme 6g]

The intermediate D synthesized in step 4) and 2,4-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ 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, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate E-3 (yield: 75%).

Step 8) Synthesis of Intermediate F-1

 [Scheme 6h]

Intermediate E-1 and triphenylphosphine synthesized in step 5) were dissolved in o -dichlorobenzene and refluxed for 24 hours. At the end of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate F-1 (yield: 58%).

Step 9) Synthesis of Intermediate F-2

 Scheme 6i

Intermediate E-2 and triphenylphosphine synthesized in step 6) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate F-2 (yield: 56%).

Step 10) Synthesis of Intermediate F-3

 Scheme 6j

Intermediate E-3 and triphenylphosphine synthesized in step 7) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate F-3 (yield: 59%).

Step 11 ) Synthesis of Intermediate G-1

 [Scheme 6k]

The intermediate F-2 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 9) 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 removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired intermediate G-1 (yield: 73%).

Step 12 ) Synthesis of Intermediate G-2

 Scheme 6l

The intermediate F-3 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 10) 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 removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was purified by column chromatography to give the desired intermediate G-2 (yield: 77%).

Synthesis example) Subgenuse  1 (compound 4 )of Example

 Scheme 7

The intermediate F-1 and Iodobiphenyl, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 8) 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 desired compound 4 by column chromatography (yield: 63%).

Synthesis example) Subgenuse  2 (compound 34 )of Example

 Scheme 8

Intermediate G-1 synthesized in step 11) and 4- (1-Phenyl-1 H- benzo [ d ] imidazol-2-yl) phenylboronic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ After dissolving in a small amount of water, it was refluxed for 24 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 34 using the column chromatography (yield: 55%).

Synthesis example) Subgenuse  3 (compound 50 )of Example

 Scheme 9

The intermediate G-2 synthesized in step 12) and 2-Naphthylboronic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 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 50 by column chromatography (yield: 68%).

Synthesis example) Subgenuse  4 (compound 85 )of Example

 Scheme 10

Intermediate G-1 synthesized in step 11) and N- (Biphenyl-4-yl) -9,9-dimethyl-9 H -fluoren-2-amine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu was dissolved in Toluene solvent and stirred at 110 ° C. for 24 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 85 by column chromatography (yield: 61%).

Synthesis example) Subgenuse  5 (compound 101 )of Example

 Scheme 11

Intermediate G-2 and Dibiphenyl-4-ylamine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 12) were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. I was. 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 101 by column chromatography (yield: 66%).

abandonment EL  Manufacturing evaluation of the device

Various compounds obtained through synthesis were used as light emitting host materials and hole transport layer materials of the light emitting layer, respectively, to fabricate an organic light emitting display device according to a conventional method. A copper phthalocyanine (hereinafter abbreviated as CuPc) film was first vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

When measured as a luminescent host material, 30 nm of 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as a-NPD) as a major transport compound on this film was measured. The hole transport layer was formed by vacuum deposition to a thickness of. After the hole transport layer was formed, tris (2-phenylpyridine) iridium (abbreviated as I r (ppy) ₃ hereinafter) was added as a phosphorescent Ir metal complex dopant on the hole transport layer. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. Into the hole blocking layer, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, followed by electron injection. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was deposited into the layer to a thickness of 40 nm. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, Al was deposited to a thickness of 150 nm, and the organic electroluminescent device was manufactured by using this Al / LiF as a cathode.

When measuring as a hole transport layer material, a light emitting material doped with BD-052X (Idemitus) 7% doped with a thickness of 45 nm was used. In this case, BD-052X is a blue fluorescent dopant, and an organic light emitting diode was manufactured using 9,10-di (naphthalen-2-yl) anthracene (ADN) as a light emitting host material.

Comparative Experimental Example  One

Of the synthesized compounds, compounds 4, 34 and 50, respectively, were used as luminescent host materials. For comparison, an organic electroluminescent device having the same structure as the test example was manufactured by using a compound represented by Chemical Formula 6 (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

The physical properties of the organic electroluminescent device of Comparative Example 1 and the organic electroluminescent device of Experimental Example using CBP as a host material are summarized in Table 1 below.

Emitting layer
Host substance Voltage
(V) Current density
( mA Of cm ² ) Luminous efficiency
(㏅ / A) Chromaticity coordinates
(x, y) Example 1 Compound 4 5.2 0.30 50.5 (0.31, 0.61) Example 2 Compound 34 5.0 0.31 55.2 (0.32, 0.61) Example 3 Compound 50 5.5 0.32 48.3 (0.30, 0.60) Comparative Example 1 CBP 5.1 0.31 32.6 (0.33, 0.61)

As can be seen from Table 1, the organic electroluminescent devices of Experimental Examples 1 to 3 exhibited substantially the same color coordinates compared to the organic electroluminescent devices using CBP as a host material, and improved luminous efficiency with critical significance. Able to know.

Comparative Experimental Example  2

Compounds 85 and 101, respectively, of the synthesized compounds were used as hole transport layer materials. For comparison, an organic electroluminescent device having the same structure as the test example was manufactured using a compound represented by the following Chemical Formula 7 (hereinafter abbreviated as a-NPB) as a hole transport material instead of the compound of the present invention.

The physical properties of the organic electroluminescent device of Comparative Example 2 and the organic electroluminescent device of Experimental Example using a-NPD as the hole injection layer material are summarized in Table 2 below.

Hole transport layer
matter Voltage
(V) Current density
( mA Of cm ² ) Luminous efficiency
(㏅ / A) Chromaticity coordinates
(x, y) Example 4 Compound 85 6.1 12.55 8.6 (0.15, 0.14) Example 5 Compound 101 6.2 12.77 8.3 (0.15, 0.15) Comparative Example 2 a-NPB 7.2 13.35 7.5 (0.15, 0.15)

As can be seen from Table 2, the organic electroluminescent devices of Experimental Examples 4 and 5 exhibit substantially the same color coordinates as the organic electroluminescent device using a-NPB as the hole transport layer material, and have the driving voltage, the current density, and the light emission. It can be seen that the efficiency has improved with critical significance.

Based on the above results, the compounds of the present invention have excellent electrical and light emission characteristics, and thus, when used in organic light emitting diodes as hole injection materials and hole transport materials, high-efficiency, Low voltage, high brightness and long life can be expected. In addition, since green and blue light emission of long life is obtained, it is used as a green phosphorescent host material and a hole transport layer material of the organic light emitting device, and thus it is possible to remarkably improve the luminous efficiency and lifetime. On the other hand, it is apparent that the compounds of the present invention can achieve the same effect even when used in other organic material layers of the organic light emitting device.

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.

Claims (12)

A compound represented by the following formula;

(1) R ₁ , R ₂ , R ₃ and R ₄ are each independently or unsubstituted alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted carbon number 1 An alkenyl group of 60 to 60, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group of 5 to 60 carbon atoms, sulfur (S), Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O ) Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one of phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) And a substituted or unsubstituted C 1 to C 60 heteroaryloxy group containing at least one silicon (Si).
(2) R _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number An alkoxy group of 1 to 60, a substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one of 5 to 60 aryloxy groups, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); or Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) A substituted or unsubstituted carbon having 1 to 60 carbon atoms containing at least one of (N), oxygen (O), phosphorus (P) and silicon (Si). Roatan is rilok time.
(3) Ar ₁ is a hydrogen atom, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, substituted or unsubstituted Substituted or unsubstituted carbon atoms having 1 to 50 carbon atoms containing at least one aryl group having 5 to 60 ring carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one alkyl group or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) , A substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).
(3) Said n is an integer of 1-4. The method of claim 1,
The compound is,

or

Is indicated by
Ar ₁ is as defined above, Ar ₂ is a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, Substituted or unsubstituted carbon atoms containing at least one substituted or unsubstituted aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) 1 Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur containing at least one alkyl group of 50 to 50 or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). It is a substituted or unsubstituted C1-C60 heteroaryloxy group containing at least one (S), nitrogen (N), oxygen (O), phosphorus (P), and silicon (Si). The method of claim 1,
The compound is,

or

Is indicated by
Ar ₁ is as defined above, and R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number An alkoxy group of 1 to 60, a substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one of 5 to 60 aryloxy groups, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); or Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substituted or unsubstituted at least one containing (N), oxygen (O), phosphorus (P) and silicon (Si) Having 1 to 60 carbon atoms is a hetero aryloxy group. The method of claim 1,
The compound is,

Is indicated by
Ar ₁ is as defined above, and R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number An alkoxy group of 1 to 60, a substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one of 5 to 60 aryloxy groups, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); or Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substituted or unsubstituted at least one containing (N), oxygen (O), phosphorus (P) and silicon (Si) Having 1 to 60 carbon atoms is a hetero aryloxy group. The method of claim 1,
R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ combine with an adjacent group to form a substituted or unsubstituted ring. The method according to any one of claims 1 to 4,
Said compound being used in a soluble process. An organic electronic device comprising at least one organic material layer containing a compound of any one of claims 1 to 4. The method of claim 7, wherein
The organic electronic 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 includes a hole injection layer, a hole transport layer, a light emitting layer and an electron injection layer, wherein the compound of claim 1 is included in one or more of the hole injection layer and the hole transport layer. 10. The method of claim 9,
The compound is an organic electronic device, characterized in that used as a fluorescent host material containing blue, green, red, white in the light emitting layer. 10. The method of claim 9,
The organic electronic device of claim 1, wherein the compound of any one of claims 1 to 4 is formed by a soluble process. A display device comprising the organic electronic device of claim 7;
And a control unit for driving the display device.

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