WO2013183904A1 - Compound containing benzofluorene for organic electronic device, and organic electronic device and electronic apparatus using same - Google Patents

Abstract

The present invention relates to a compound containing a benzofluorene compound and a derivative thereof for an organic electronic device, and to an organic electronic device and an electronic apparatus using same. According to the present invention, light-emitting efficiency, color purity, and the life of a device can be improved and driving voltage can be reduced.

Description

Compound for organic electric element containing benzofluorene, organic electric element using same and electronic device thereof

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 emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. 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 a hole transporting layer or a buffer layer for excellent life characteristics of the organic electric device, and for this, a thin film after deposition while giving high hole transporting 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 light emission wavelength is shifted to the long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of dopant having an energy band gap smaller than that of the 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 of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be 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 device has not been made sufficiently, and therefore, the development of new materials is still 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.

Formula 1

In the above formula,

(1) Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, tritium, halogen, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, In the group consisting of C ₆ ~ C ₂₀ aryl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group C ₁ ~ C ₅₀ alkyl group unsubstituted or substituted with a selected substituent;

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 an acetylene group, 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 C ₂ ~ C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene 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 ₁ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Aryloxy 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Arylsilyl 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 C ₆₀ aryl group; Is selected from the group consisting of

(2) L ₁ and L ₂ are each independently of the other,

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 C ₆ ~ C ₆₀ arylene group unsubstituted or substituted with a substituent;

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 A substituted or unsubstituted C ₃ ~ C ₆₀ hetero arylene group; And divalent substituted or unsubstituted C ₁ to C ₆₀ aliphatic hydrocarbon group; Is selected from the group consisting of

(3) m and n are integers from 0 to 4,

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

Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; 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 C ₆₀ aryl group; 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.

Formula 2

Formula 3

Formula 4

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, "aryl group" means an aromatic monocyclic ring or polycyclic ring, 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 polycyclic ring containing hetero atoms (heteroatoms) instead of carbon forming a ring, and heteroaromatics formed by neighboring substituents participating in a bond or reaction 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, since it exhibits the effect of greatly improving the high luminous efficiency, high heat resistance, color purity and lifetime of the device, a display device, an organic electroluminescent device (OLED), an organic solar system 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.

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 addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can 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 is to be understood that the elements 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.

Example 1

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.

Table 1

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, a nitrile group and an 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 an acetylene group, 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 C ₂ ~ C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene 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 ₁ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Aryloxy 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Arylsilyl 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 C ₆₀ aryl group; 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 C ₆ ~ C ₆₀ arylene group unsubstituted or substituted with a substituent;

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;

Nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₃~ C₆₀Hetero 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.

TABLE 2

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.

Example 2

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 for 12 hours at 70 ° C. 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.

TABLE 3

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 ₁ ~ C ₅₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Alkyl groups;

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 an acetylene group, 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 C ₂ ~ C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene 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 ₁ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Aryloxy 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Arylsilyl group; And

Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl groups, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; It may be a compound selected from the group consisting of.

In addition, L in Sub 5 is 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 C ₆ ~ C ₆₀ arylene group unsubstituted or substituted with a substituent selected from the group consisting of an amino 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, 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;

Nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₃~ C₆₀Hetero arylene group; And Divalent substituted or unsubstituted C_One~ C₆₀Aliphatic hydrocarbon groups; It may be a compound selected from the group consisting of.

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

Example 3

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.

Table 4

Sub 7 is not limited to the above-listed compounds (Sub 7-1 to Sub 7-6). That is, Ar in Sub 7₂, Ar₂, L, m and n silver  Ar of Sub 5₂, Ar₂, L, m and n are the same.

Example 4

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.

Table 5

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.

Example 5

Product synthesis

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.

Example 6

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 thereto, 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 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%)

Example 7

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 thereto, 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 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%)

Example 8

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 thereto, 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 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%)

Example 9

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 thereto, 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 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.

Table 6

On the other hand, each substituent of the compounds represented by the formula (1) to formula (4) has a broad relationship, exemplarily described 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.

Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. 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 is formed by using various 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 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 light emitting 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 a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

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

In addition, the organic 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 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), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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 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, 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 and 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 control, a navigation device, a game machine, various TVs, various computers, and the like.

Manufacturing Evaluation of Organic Electrical Device

EXAMPLES Examples (1) to (213)

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) ), A light emitting layer doped with 450% thick BD-052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant, and the light emitting host material is one of compounds 1-1 to 3-71) Then, the electron transport layer (electron transport layer material: Tris (8-quinolinolato) aluminum (Alq ₃ )) having a thickness of 250 kPa, the electron injection layer (LiF) having a thickness of 10 kW, and the 1500 kW thick Aluminum cathodes were sequentially deposited to fabricate an organic electroluminescent device.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example, except that ADN was used as a light emitting host material using the compound of the present invention.

<ADN>

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example, except that Compound A was used as a light emitting host material using the compound of the present invention.

<Compound A>

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example, except that Compound B was used as a light emitting host material using the compound of the present invention.

<Compound B>

[Example I] The photoresearch was performed by applying a forward bias DC voltage to the organic light emitting diodes of Examples (1) to (213) and Comparative Examples (1) to (3). The electroluminescence (EL) characteristics were measured with PR-650, and the T90 life was measured using the life-time measurement equipment manufactured by McScience Inc. at 300 cd / m2 reference luminance.

Table 7 shows the device fabrication and evaluation results of Examples (1) to (213) and Comparative Examples (1) to (3) 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).

[Revision under Rule 26 02.07.2013]
TABLE 7

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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, Compound A of Comparative Example (2) and Compound B of Comparative Example (3) having benzofluorene than ADN used in Comparative Example (1) improved the luminous efficiency and lifetime more, The compounds of the present invention in which the fluorene was fused at Nos. 2 and 3 more efficiently than the Compound A of Comparative Example (2) and the Compound B of Comparative Example (3) where the fused position is 3, 4 And it can be seen that the life is significantly improved.

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.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, 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.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority to US Patent Application No. 10-2012-0060940, filed with Korea on 07/07/2012, in accordance with United States Patent Act Section 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (11)

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

              <Formula 1>

   

   In the above formula,

   (1) Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, tritium, halogen, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, In the group consisting of C ₆ ~ C ₂₀ aryl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group C ₁ ~ C ₅₀ alkyl group unsubstituted or substituted with a selected substituent;

   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 an acetylene group, 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 C ₂ ~ C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene 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 ₁ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Aryloxy 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 ₆ ~ C ₃₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Arylsilyl 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 C ₆₀ aryl group; Is selected from the group consisting of

   (2) L ₁ and L ₂ are each independently of the other,

   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 C ₆ ~ C ₆₀ arylene group unsubstituted or substituted with a substituent;

   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;

   Nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₃~ C₆₀Hetero arylene group; And Divalent substituted or unsubstituted C_One~ C₆₀Aliphatic hydrocarbon groups; 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, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; 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 C ₆₀ aryl group; It 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.
2. 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.
3. The method of claim 1,

   The compound is an organic electronic device compound represented by any one of the following formula (2).

   
4. The method of claim 1,

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

   

   

   

   

   

   
5. 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.
7. The method of claim 5,

   An organic electric device comprising a first electrode, the organic material layer and a second electrode sequentially stacked.
8. 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.
9. The method of claim 8,

   The compound is an organic electroluminescence device, characterized in that used as the light emitting layer material.
10. A display device comprising the organic electroluminescent device of claim 5; And

    A controller for driving the display device; Electronic device comprising a.
11. 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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