KR20130137384A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

The present invention relates to a compound for an organic electronic element including a benzo fluorine compound and a derivative thereof, an organic electronic element utilizing the same, and an electronic device thereof. According to the present invention, the light emitting efficiency, the color purity, and the lifetime of the organic electronic element can be improved, and a driving voltage of the organic electronic element can be lowered. [Reference numerals] (401) Substrate;(402) Anode;(404) Hole transport layer;(405) Light-emitting layer;(406) Electron transport layer;(408) Cathode

Description

Compound for organic electric device containing benzofluorene, organic electronic device using same and electronic device thereof TECHNICAL FIELD OF THE INVENTION, AND A ELECTRONIC DEVICE THEREOF}, ORGANIC ELECTRONIC ELEMENT USING THE SAME

The present invention relates to a compound for an organic electric device comprising benzofluorene and its derivatives, an organic electric device comprising the same, and an electronic device thereof.

Mr. Eastman Kodak Corporation in the 1980s. W. C. W. Tang et al. Developed a laminated structure element in which various roles were distributed to each material, thereby making organic electroluminescent elements using organic materials practical. They stacked phosphors that could transport electrons and organics that could transport holes, and injected both charges into a layer of the phosphor to emit light, so that high brightness of 1000 cd / m2 or more could be obtained at a voltage of 10 V or less. .

Conventional liquid crystal display, which is a typical flat panel display device, can be lighter than conventional cathode ray thbe (CRT), but has a problem in that a viewing angle is limited and a back light is necessarily required. However, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, application to full-color display or lighting is expected.

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. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed 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 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.

In particular, various studies have been conducted on organic materials inserted into the hole transport layer or the buffer layer for excellent life characteristics of the organic electric device, and for this purpose, a thin film after deposition is provided while providing high hole transport characteristics from the anode to the organic layer. There is a need for a hole injection layer material having high uniformity and low crystallinity in forming.

Delays penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, and stable properties for Joule heating generated when driving the device, that is, high glass transition temperature. There is a need for development of a hole injection layer material having In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer 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 above-described organic electroluminescent device, a material constituting 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.

An object of the present invention is to provide an organic electric device using the benzofluorene compound and its derivatives, which can improve the high luminous efficiency, high heat resistance, color purity and lifetime of the device, and a terminal thereof.

Specifically, the present invention provides a compound represented by the following formula (1) to solve the problems of the prior art described above, and to achieve the object of the present invention to improve the luminous efficiency, high heat resistance, color purity, stability and life of the device do.

In the above formulas,

(1) Ar ₁ And Ar ₂ is a C ₆ substituted with each another independently hydrogen, deuterium, tritium, a halogen group, an aryl group, a heavy hydrogen of C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the Substituted or unsubstituted by a substituent selected from the group consisting of an aryl group of ~ C _20, an arylalkyl group of C ₇ ~ C ₂₀ , an aryl alkenyl group of C ₈ ~ C ₂₀ , a heterocyclic group of C ₂ ~ C ₂₀ , a nitrile group and an acetylene group Substituted C ₁ to C ₅₀ alkyl group;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryl silyl group; And

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, and a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to an aryl group of C _60; Is selected from the group consisting of

(2) L ₁ And L ₂ are each independently of one another,

Selected from the group consisting of nitro, nitrile, halogen, silane, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group substituted with a substituent or unsubstituted aryl group of C ₆ ~ C _60;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;

A substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group Substituted or unsubstituted C ₃ ~ C ₆₀ Hetero arylene group ; And Divalent substituted or unsubstituted aliphatic hydrocarbon group; Is selected from the group consisting of

(3) m and n are integers of 0-4,

(4) R ' and R " are each independently hydrogen;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ An alkyl group; And

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, and a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to an aryl group of C _60; It is selected from the group consisting of, these can combine with each other to form a spiro compound,

(5) Each of R ' , R ", Ar ₁ and Ar ₂ may be bonded or reacted with groups adjacent to each other to form a substituted or unsubstituted saturated or unsaturated ring.

In Chemical Formulas 2 to 4

(1) R ' , R ", Ar ₁ and Ar ₂ are the same as R' , R", Ar ₁ and Ar ₂ defined in Chemical Formula 1.

As used herein, an "aryl group" refers to a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spiro fluorene group.

In addition, a "heterocyclic group" means an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom (heteroatom) instead of a carbon forming a ring, a hetero formed by neighboring substituents participating in the bond or reaction Aromatic or cycloaliphatic rings.

More specifically, Chemical Formulas 1 to 4 may be one of the following compounds, but are not limited thereto.

The compounds represented by Chemical Formulas 1 to 4 may be one of the compounds shown above, but are not limited thereto. In this case, since it is practically difficult to exemplify all compounds in a wide relationship with each substituent of the compounds represented by the formulas (1) to (4), the exemplary compounds have been described by way of example, but the compounds represented by the formulas (1) to (4) not shown Part of this specification may be constituted.

In still another aspect, the present invention provides an organic electric element using the compound represented by the above formula and an electronic device including the organic electric element.

By using the benzofluorene and its derivatives according to the present invention, the display device, the organic electroluminescent device (OLED), and the organic solar cell are exhibited since the luminescence efficiency, high heat resistance, color purity and lifetime of the device can be greatly improved. It can be usefully used in batteries, organophotoreceptors (OPC), organic transistors (organic TFTs) and lighting.

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

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if 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 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. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

Hereinafter, the preparation or synthesis examples of some of the compounds belonging to Formulas 1 to 4 will be described. However, since the number of the compounds belonging to the general formula (1) to formula 4 is a large number of them will be described by way of example. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.

General Synthesis Example

Among the general synthesis methods exemplified above, "Sub 1 + Sub 2 → Sub 3" synthesis, "Sub 3 + Sub 4 → Sub 5" synthesis and "Sub 5 + Sub 6 → Sub7" synthesis, based on the Suzuki cross-coupling reaction, Herrmann, WA The Suzuki cross-coupling. Applied Homogeneous Catalysis with Organometallic Compounds (2nd Edition) 2002 , 1, 591-598. And Jones, WD Synthetic chemistry: The key to successful organic synthesis is. Science 2002 , 295, 289-290. And the like.

Sub  3 Synthesis

After mixing 1,4,6-tribromonaphthalene Sub 1 (1 equiv) and Sub 2 (1 equiv) to THF in a round flask, add Pd (PPh ₃ ) ₄ (0.05 equiv) and aqueous NaOH solution. After stirring for some time and refluxing, the mixture was extracted with MC and water, and then the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain product Sub 3.

An example of Sub 2 is as follows, but is not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 2-1 to Sub 2-12, and the results are as follows.

Sub 2 is not limited to the above-listed compounds (Sub 2-1 to Sub 2-12), that is, Ar ₂ of Sub ₂ is hydrogen, deuterium, tritium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, C of C ₁ ~ C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryl silyl group; And

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to an aryl group of C _60; It may be a compound selected from the group consisting of.

In addition, L of Sub 2 is

Selected from the group consisting of nitro, nitrile, halogen, silane, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group substituted with a substituent or unsubstituted aryl group of C ₆ ~ C _60;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;

Substituted by a substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and amino group Or an unsubstituted C ₃ ~ C ₆₀ hetero arylene group And Divalent substituted or unsubstituted aliphatic hydrocarbon group ; It may be a compound selected from the group consisting of.

In addition, m of Sub2 is an integer of 0-4.

An example of Sub 3 is as follows, but is not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 3-1 to Sub 3-6, and the results were as follows.

Sub 3 is not limited to the above-listed compounds (Sub 3-1 to Sub 3-6). That is, Ar _2, L, m of Sub 3 are the same as Ar _2, L, m 2 of the Sub.

Sub  5 Synthesis

After mixing in an amount corresponding to Sub 3 (1 equivalent), Sub 4 (1 equivalent) and THF in a round flask, Pd (PPh ₃ ) ₄ (0.05 equivalent) and an aqueous NaOH solution were added thereto, followed by stirring under reflux at 70 ° C. for 12 hours. After extracting with MC and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product Sub 5.

An example of Sub 4 is the same as Sub 2, but is not limited thereto. That is, Ar ₁ of Sub 4 is equal to Ar ₂ of Sub 2, L of Sub 4 is equal to L of Sub 2, and n of Sub 4 is equal to m of Sub 2.

An example of Sub 5 is as follows, but is not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 5-1 to Sub 5-6, and the results were as shown in Table 3 below.

Sub 5 is not limited to the above-listed compounds (Sub 5-1 to Sub 5-6). That is, Ar ₁ and Ar ₂ of Sub 5 are each independently of each other.

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ An alkyl group;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryl silyl group; And

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ alkynyl group of ₂₀ ~ C aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, an arylalkenyl group of C ₈ ~ C _20, a silane group, a boron group, a germanium group, an aryl group of C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ ~ C ₆₀ of; It may be a compound selected from the group consisting of.

In addition, L of Sub 5 is

Selected from the group consisting of nitro, nitrile, halogen, silane, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group and C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group, amino group substituted with a substituent or unsubstituted aryl group of C ₆ ~ C _60;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;

Substituted by a substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and amino group Or an unsubstituted C ₃ to C ₆₀ hetero arylene group ; And Divalent substituted or unsubstituted aliphatic hydrocarbon group; It may be a compound selected from the group consisting of.

In addition, m, n of Sub 5 may be an integer of 0 to 4, respectively.

Sub  7 Synthesis

After mixing in an equivalent amount of Sub 5 (1 equivalent), Sub 6 (1 equivalent) and THF in a round flask, Pd (PPh ₃ ) ₄ (0.05 equivalent) and an aqueous NaOH solution were added thereto, followed by stirring under reflux for 12 hours at 70 ° C. After extraction with MC and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the product Sub 7.

An example of Sub 7 is as follows, but is not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 7-1 to Sub 7-6, and the results were as shown in Table 4 below.

Sub 7 is not limited to the above-listed compounds (Sub 7-1 to Sub 7-6). That is, Ar ₂ , Ar ₂ , L, m and n of Sub 7 Is the same as Ar ₂ , Ar ₂ , L, m and n of Sub 5.

Sub  8 Synthesis

Add Sub 7 to a 500 mL two-necked round bottom flask, add chlorobenzene and PPA and stir at room temperature for 12 hours. Water was added to the reaction mixture, stirred for 10 minutes, and then the organic layer and the water layer were separated. After extraction with normal hexane, the water of the organic solvent layer is removed using MgSO ₄ and dried under reduced pressure to remove the solvent. The crude product thus obtained was separated and purified through silica gel column chromatography using normal hexane to obtain Sub 8.

An example of Sub 8 is as follows, but is not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 8-1 to Sub 8-6, and the results were as shown in Table 5 below.

Sub 8 is not limited to the above-listed compounds (Sub 8-1 to Sub 8-6). That is _{Ar 2, Ar 2, L,} m and n of the Sub 8 is the same as that of the _{Sub 5 Ar 2, Ar 2,} L, m and n.

Product  Synthetic method

Sub 8 is added to a 250 mL 2-necked round bottom flask and dissolved with THF as a solvent. The reaction temperature was lowered to -78 ° C and n-BuLi at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered back to -78 ° C, iodomethane was added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, water was added, followed by extraction with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting product was purified by silica gel column chromatography using ethyl acetate and normal hexane.

Product  1-5 Synthesis Example

Into a 250 mL round bottom flask, add 2- (4- (9-phenyl-11H-benzo [b] fluoren-6-yl) phenyl) pyridine (25.0 mmol, 11.1 g) and dissolve in 125 mL of THF. After the temperature was lowered to -78 ° C, n-BuLi (25.0 mmol, 10 mL) at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered to -78 ° C again and iodomethane (62.5 mmol, 8.87 g) was added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added, and the mixture was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting compound was purified by silica gel column chromatography using ethyl acetate and normal hexane to give 5.88 g of the final compound. (Yield 68%)

Product  2-26 Synthesis Example

6- (naphthalen-1-yl) -9- (4- (naphthalen-2-yl) phenyl) -11H-benzo [b] fluorene (25.0 mmol, 13.6 g) was added to a 250 mL round bottom flask, and 125 mL of THF as a solvent. Dissolve by adding After the reaction temperature was lowered to -78 ° C, n-BuLi (25.0 mmol, 10 mL) at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered to -78 ° C again and iodomethane (62.5 mmol, 8.87 g) was added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added, and the mixture was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting compound was purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain 10.0 g of a final compound. (Yield 70%)

Product  2-49 Synthesis Example

Add 9- (4- (naphthalen-1-yl) phenyl) -6- (naphthalen-2-yl) -11H- (25.0 mmol, 13.6) to a 250 mL round bottom flask, and add 125 mL of THF as a solvent to dissolve it. The reaction temperature was lowered to -78 ° C, and 2.5M n-BuLi (25.0 mmol, 10 mL) was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered to -78 ° C again and iodomethane (62.5 mmol, 8.87 g) was added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added, and the mixture was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting compound was purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain 10.2 g of the final compound. (Yield 71%)

Product  3-16 Synthesis Example

6,9-bis (4-methoxyphenyl) -11H-benzo [b] fluorene (25.0 mmol, 11.1 g) is added to a 250 mL round bottom flask, and 125 mL of solvent THF is added to dissolve it. After the reaction temperature was lowered to -78 ° C, n-BuLi (25.0 mmol, 10 mL) at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered to -78 ° C again and iodobenzene (62.5 mmol, 12.8 g) was added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added, and the mixture was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting compound was purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain 10.3 g of the final compound. (Yield 71%)

Mass spectrometry (HRMS) was carried out on the compounds Sub 1-1 to Sub 3-24, and the results were as shown in Table 6 below.

On the other hand, each substituent of the compounds represented by the formula (1) to formula (4) has a broad relationship, by way of example to explain the synthesis examples of the representative compounds, compounds that are not illustratively described as a synthesis example will also form part of the present specification. Can be.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.

The compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.

The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.

The organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.

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

Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

The organic electroluminescent element in which the compounds of the present invention can be used is, for example, for a display device, an organic electroluminescent element (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), monochrome or white illumination. Element;

As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.

Another embodiment of the present invention is an organic electroluminescent 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 comprises an organic electroluminescent device comprising the compounds of the present invention to provide.

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

The organic electroluminescent 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, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures.

1 to 6, the organic electroluminescent device includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and at least one layer of the organic material layer except for the light emitting layer may be omitted.

Although not shown, the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound of the present invention 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 of the present invention is used in place of or in combination with one or more of 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, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.

For example, the organic electroluminescent device according to another embodiment of the present invention is a metal having 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 layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.

The substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a 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. The positive electrode material may be a material having a large work function to facilitate hole injection 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 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.

The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, 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, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.

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 may be a material having good quantum efficiency for fluorescence or phosphorescence.

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) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (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 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. .

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 Alq3; 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. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function 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, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.

The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on 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.

Evaluation of manufacturing of organic electric device

An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting layer material. First, a 600 Å thick hole injection layer on the ITO layer (anode) formed on the glass substrate (hole injection layer material: 4,4'4 "-tris [2-naphthyl (phenyl) amino] -triphenylamine (2-TNATA )), a hole transport layer of 300Å thickness (the hole transport layer material: N ^4, N ^{4 '-} di ^{(naphthalene-1-yl) - N 4, N 4'} - diphenyl-biphenyl-4,4'-diamine (NPB) ), And a light emitting layer (BH-052X is a blue fluorescent dopant, and the compound of the present invention as a light emitting host material) is used as a light emitting layer of BD-052X (Idemitsu Co., Ltd.) having a thickness of 450 kHz. Electron transport layer material: Tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode were sequentially deposited to form an organic electroluminescent device. Produced.

For comparison, Comparative Example (1) (abbreviated as ADN), Comparative Example (2), and Comparative Example (3) represented by the following formula instead of the compound of the present invention was used as the light emitting layer material, An organic electroluminescent device was manufactured.

Comparative Example (1) Comparative Example (2) Comparative Example (3)

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices prepared as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measured results were measured at 300 cd / m2 reference luminance. The T90 life was measured using a life measurement instrument manufactured by McScience.

Table 7 shows the fabrication of devices and evaluation results of Examples and Comparative Examples to which the compounds according to the invention are applied. In Table 7 below, Compound A is Comparative Example (2) Compound 7,7-dimethyl-5- (4- (10-phenylanthracen-9-yl) phenyl) -7H-benzo [c] fluorene, and Compound B was compared Corresponds to compound 7,7-dimethyl-5- (4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -7H-benzo [c] fluorene in Example (3).

As can be seen from the results of Table 7, the organic electroluminescent device using the organic electroluminescent device material of the present invention can be used as a light emitting layer material can significantly improve the high luminous efficiency, lifetime and color purity.

In other words, Comparative Examples (1) and Comparative Examples (3) having benzofluorene than Comparative Example (1) (ADN) further improved luminous efficiency and lifetime, and the fused position of fluorene was 3, It can be seen that the compounds of the present invention, which are fused at Nos. 2 and 3, compared to Comparative Example (2) and Comparative Example (3), which are at position 4, significantly improve efficiency and lifespan.

On the other hand, because of the excellent properties as described above, the compound of the present invention is not only an organic electroluminescent device (OLED), but also a display device, an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination Or the like.

The same effect can be obtained even when the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a light emission auxiliary layer.

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 scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (11)

Compound for an organic electric device comprising a compound represented by the formula (1).
≪ Formula 1 >

In the above formulas,
(1) Ar ₁ And Ar ₂ are each independently hydrogen, deuterium, tritium, halogen, alkenyl group of C ₂ ~ C ₂₀ , alkoxy group of C ₁ ~ C ₂₀ , aryl group of C ₆ ~ C ₂₀ , C substituted with deuterium Substituted with a substituent selected from the group consisting of ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted C ₁ ~ C ₅₀ Alkyl group;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryl silyl group; And
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, and a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to Aryl group of C ₆₀ ; Is selected from the group consisting of
(2) L ₁ And L ₂ are each independently of one another,
Selected from the group consisting of nitro, nitrile, halogen, silane, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group substituted with a substituent or unsubstituted aryl group of C ₆ ~ C _60;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;
A substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group Substituted or unsubstituted C ₃ ~ C ₆₀ Hetero arylene group ; And Divalent substituted or unsubstituted aliphatic hydrocarbon group; Is selected from the group consisting of
(3) m and n are integers of 0-4,
(4) R ' and R " are each independently hydrogen;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ An alkyl group; And
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, and a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to Aryl group of C ₆₀ ; Is selected from the group consisting of R ' And R ” may combine with each other to form a spiro compound,
(5) Each of R ' , R ", Ar ₁ and Ar ₂ may be bonded or reacted with groups adjacent to each other to form a substituted or unsubstituted saturated or unsaturated ring. The method of claim 1,
The R ′ , R ″, Ar ₁ and Ar ₂ are each bonded to or reacted with a group adjacent to each other to form a saturated or unsaturated ring compound for an organic electric device. The method of claim 1,
The compound is an organic electronic device compound represented by any one of the following formula (2).
&Lt; Formula 2 >< EMI ID =

The method of claim 1,
Compound for an organic electronic device, characterized in that one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1. 6. The method of claim 5,
An organic electric device, characterized in that to form the compound to the organic material layer by a solution process. 6. The method of claim 5,
An organic electric device comprising a first electrode, the organic material layer and a second electrode sequentially stacked. 6. The method of claim 5,
The organic material layer comprises at least one of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer. The method of claim 8,
The compound is an organic electroluminescence device, characterized in that used as the light emitting layer material. A display device comprising the organic electroluminescent device of claim 5; And
A controller for driving the display device; &Lt; / RTI &gt; The method of claim 10,
The organic electronic device is one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.

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