KR101896008B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a compound for an organic electronic device including a benzofluorene compound and a derivative thereof, an organic electric device using the same, and an electronic device thereof, and the present invention can improve the luminous efficiency, color purity and lifetime of the device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for an organic electronic device including a benzofluorene compound, an organic electronic device using the compound, and an electronic device using the compound.

TECHNICAL FIELD [0001] The present invention relates to a compound for an organic electric device including a benzofluorene and a derivative thereof, an organic electric device including the same, and an electronic device thereof.

Mr. Eastman Kodak of the 1980s. W. C. W. Tang et al. Have made organic electroluminescent devices using organic materials practical by developing laminated structure devices in which various roles are shared among various materials. They emit phosphors capable of transporting electrons and organic materials capable of transporting holes, and both charges are injected into the phosphor layer to emit light, so that a luminance of 1000 cd / m 2 or more can be obtained at a voltage of 10 V or less .

A conventional liquid crystal display, which is a typical flat display device, can be made lighter than a conventional CRT (cathode ray tube), but has a problem that a viewing angle is limited and a back light is necessarily required. However, an organic light emitting diode (OLED), which is a new flat display device, is a display using self-luminescence phenomenon and has advantages such as a large viewing angle, a light weight and a small size compared to a liquid crystal display, In recent years, application to a full-color display or illumination 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.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The 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 . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

Particularly, various studies have been conducted on organic materials inserted into a hole transporting layer or a buffer layer for an excellent lifetime characteristic of an organic electric device. To this end, a high hole transporting property from an anode to an organic layer is given, A hole injection layer material having high uniformity and low crystallinity is required.

It is possible to delay penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifetime of the organic electronic device, and to stabilize the joule heating caused by driving the device, Lt; RTI ID = 0.0 > layer < / RTI > It is also reported that the low glass transition temperature of the hole transporting layer material significantly affects the lifetime of the device depending on the characteristics of the uniformity of the thin film surface collapsing during device operation. In addition, the deposition method is the mainstream in the formation of OLED devices, and a material that can withstand such a long time, that is, a material having high heat resistance characteristics, is required.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the light emitting efficiency through the light emitting layer. 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 sufficiently exhibit the excellent characteristics of the organic electroluminescent device described above, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material However, stable and efficient development of an organic material layer for an organic electric device has not yet been sufficiently developed, and therefore development of a new material is continuously required.

An object of the present invention is to provide an organic electric device using a benzofluorene compound and a derivative thereof capable of improving the light emitting 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) for solving the problems of the prior art described above and achieving the object of the present invention of improving the luminous efficiency, high heat resistance, color purity, stability and lifetime of the device do.

In the above formulas,

(1) Ar ₁ is hydrogen, deuterium, tritium, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C of ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group , A C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group, an aryl group unsubstituted C ₆ ~ C _60;

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

A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group and C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of Group ; And

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 ₁ ~ C ₅₀ in the alkyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group substituted or a substituent selected from the group consisting of An unsubstituted fluorene group ; , ≪ / RTI >

(2) Ar ₂ represents hydrogen, deuterium, tritium, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C of ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group , A C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group, an aryl group unsubstituted C ₆ ~ C _60; And

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

(3) R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, tritium, a halogen group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, A C ₆ to C ₂₀ arylalkyl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group A C ₁ to C ₅₀ alkyl group substituted or unsubstituted with a selected substituent ; And

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; , Which may combine with each other to form a spiro compound,

(4) R ₃ and R ₄ are each independently selected from the group consisting of hydrogen, deuterium, tritium, a halogen group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, A C ₆ to C ₂₀ arylalkyl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group A C ₁ to C ₅₀ alkyl group substituted or unsubstituted with a selected substituent ;

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

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the 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 An alkoxy group ;

A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group and C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of 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 An aryloxy group ; And

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; , ≪ / RTI >

(5) R ₁ To R ₄ , Ar ₁ , Ar ₂ Each may combine with or react with an adjacent group to form a substituted or unsubstituted saturated or unsaturated ring.

In order to achieve the above object, the present invention provides a compound represented by any one of the following formulas (2) to (4).

(1) Ar ₁ , Ar ₂ , R ₁ and R ₂ are the same as Ar ₁ , Ar ₂ , R ₁ and R ₂ defined in the above formula (1).

(2) R ₅ is substituted with a 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 C ₆ ~ an aryl group of C _20, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, a nitrile group, and substituted with an acetylene group a substituent selected from the group consisting or unsubstituted of alkyl group of C ₁ ~ C _50;

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

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the 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 An alkoxy group ;

A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of 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 An aryloxy group ; And

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; ≪ / RTI >

(3) n is an integer of 1 or 2;

(4) The (R ₅ ) n in the above formula (3) means that at least one R ₅ may be substituted at positions other than the 9th and 10th positions of the anthracene.

In the present specification, the term "aryl group" means a single ring or a heterocyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The term "heterocyclic group" refers to an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom in place of the ring forming carbon, and the adjacent substituent is a hetero Aromatic or alicyclic ring.

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

The compounds represented by the above Chemical Formulas 1 to 4 may be one of the compounds shown above but are not limited thereto. Since representative substituents of the compounds represented by formulas (1) to (4) are difficult to illustrate all the compounds in a wide range, representative compounds have been exemplarily described, but the compounds represented by formulas (1) to And may constitute a part of this specification.

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

The use of the benzofluorene and derivatives thereof according to the present invention has the effect of significantly improving the luminous efficiency, the high heat resistance, the color purity and the life of the device. Therefore, the display device, the organic electroluminescent device (OLED) Batteries, organic photoconductor (OPC), organic transistors (organic TFT), and illumination.

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

Hereinafter, some embodiments of the present invention will be described in detail with reference to 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, preparation examples or synthesis examples of some of the compounds belonging to the general formulas (1) to (4) will be described. However, since the number of compounds belonging to the general formulas (1) to (4) is high, some of them will be exemplarily explained. Those skilled in the art, that is, those skilled in the art, can prepare the compounds belonging to the present invention which are not illustrated through the following production examples.

Typical Synthetic Method Example

Sub 1- 1 → Sub 1-2 "synthesis," Sub 1-5 + Sub 1-6 → Sub 1 "synthesis, and" Sub 1 + Sub 2 → Product "synthesis methods in the above exemplified general synthesis method are Suzuki cross- 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.

In addition, the synthesis method of "Br-Ar ₂ → Sub 2" is based on the Miyaura boration reaction. Ishiyama, T., Itoh, Y., Kitano, T., Miyaura, N. Synthesis of arylboronates via the palladium ) -catalyzed cross-coupling reaction of tetra (alkoxo) diborons with aryl triflates. Tetrahedron Lett. 1997, 38, 3447-3450. And the like.

Sub  1 synthesis method

Sub  1-1 Synthesis

1,5-dibromonaphthalene was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M in hexane) was slowly added dropwise, and the reaction was stirred for 30 minutes. The temperature of the reaction was lowered to -78 ° C and triisopropylborate was added dropwise. After stirring at room temperature, dilute with water and add 2 N HCl. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was recrystallized to obtain the desired Sub 1-1. (Yield: 78%).

Sub  1-2 Synthetic method

After the Sub 1-1 (1 eq.) Obtained in the above Synthesis was dissolved in THF, methyl 5-chloro-2 -iodobenzoate (1.5 _{equiv.), Pd (PPh 3) 4} (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain the product Sub 1-2. (Yield: 71%).

Sub  1-3 Synthetic method

Sub 1-2 (1 equivalent) obtained in the above synthesis was dissolved in methanesulfonic acid (50 equivalents) and stirred at 50-60 占 폚. When the reaction was completed, the temperature was lowered to 0 < 0 > C, water was added, and the precipitated solid was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to give product Sub 1-3. (Yield: 85%).

Sub  1-4 Synthetic methods

Sub 1-3 (1 equivalent) obtained in the above synthesis was dissolved in ethylene glycol, and then hydrazine monohydrate (30 equivalents), KOH (2.5 eq.) And stirred at 185 < 0 > C. When the reaction was completed, the temperature was lowered to 0 < 0 > C, water was added, and the precipitated solid was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to give product Sub 1-4. (Yield: 92%).

Sub  1-5 Synthetic methods

Sub 1-4 (1 eq) and KO t -Bu (3 eq) obtained in the above synthesis were dissolved in DMSO, stirred at 0 ° C for 5 minutes, (3 eq). After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain product Sub 1-5. (Yield: 90%).

R in RI is the same as R ₁ and R ₂ described in formula (1), specifically methyl, phenyl and the like. When R is phenyl, a ring can be formed to form a spiro bond.

Sub  1 synthesis method

After the Sub 1-5 (1.5 eq.) Obtained in the above Synthesis was dissolved in THF, Sub 1-6 (1 _{eq.), Pd (PPh 3) 4} (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain product Sub 1.

Examples of Sub 1-6 are as follows, but are not limited thereto.

As a result of performing mass spectrometry (HRMS) on the compounds Sub 1-6-1-1 to Sub 1-6-3-16, the results are shown in Table 1 below.

Sub 1-6 is not limited to the above-mentioned compounds (Sub 1-6-1-1 to Sub 1-6-3-16). In other words, Sub 1-6 of Ar ₁ is selected from hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ of for C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the 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 consisting of a heteroaryl ring selected from the group of Substituted or unsubstituted A C ₆ to C ₆₀ aryl group;

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

A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group and C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of group; And

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 ₁ ~ C ₅₀ in the alkyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group substituted or a substituent selected from the group consisting of An unsubstituted fluorene group; ≪ / RTI > and the like.

In addition, Sub 1-6 R ₃ and R ₄ are each independently selected from the group consisting of hydrogen, deuterium, tritium, a halogen group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, A substituent selected from the group consisting of a C ₆ to C ₂₀ aryl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group and an acetylene group A substituted or unsubstituted C ₁ to C ₅₀ alkyl group;

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

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and A C ₂ -C ₂₀ alkenyl group substituted or unsubstituted 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, Substituted or unsubstituted C ₁ -C ₃₀ alkyl group substituted or unsubstituted with a substituent selected from the group consisting of a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C ₂₀ arylalkenyl group, a C ₂ -C ₂₀ heterocyclic group, a nitrile group and an acetylene group, An alkoxy group;

A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group and C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of 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 substituted or unsubstituted aryl groups substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl groups, C ₈ -C ₂₀ arylalkenyl groups, C ₂ -C ₂₀ heterocyclic groups, nitrile groups and acetylene groups, An aryloxy group; And

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; in Lt; RTI ID = 0.0 > of: < / RTI >

Sub  2 synthesis method

After dissolving the bromine compound (1 eq.) In DMF, Bis (pinacolato) diboron (1.1 eq.), Pd (dppf) Cl ₂ (0.03 mmol) (3 eq.) Was added thereto, followed by stirring at 90 to 100 ° C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to give product Sub 2.

Examples of Sub 2 are as follows, but are not limited thereto.

The results of performing the mass spectrometry (HRMS) on the compounds Sub 2-1 to Sub 2-35 were as shown in Table 2 below.

Sub 2 is not limited to the above-mentioned compounds (Sub 2-1 to Sub 2-34). That is, Ar ₂ of Sub 2 is hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkoxy group of C ₂₀ alkyl group, C ₁ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ A C ₂ to C ₂₀ alkenyl group, a C ₂ to C ₂₀ alkynyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ substituted or unsubstituted C ₆ to C ₂₀ arylthio group, An aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, an arylalkenyl group having a C ₈ to C ₂₀ aryl group, a silane group, a boron group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group A substituted or unsubstituted C ₆ -C ₆₀ aryl group; And

Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and is unsubstituted or substituted with a substituent selected from the group consisting of acetylene, O, N, S, Si , C 2 ~ C ₆₀ heteroaryl rings containing at least one hetero atom of the group P; in Lt; RTI ID = 0.0 > of: < / RTI >

Product  Synthetic method

Sub 1 compound (1 equivalent) obtained in the above synthesis was dissolved in Toluene. Sub 2 compound (1.1 equivalent), Pd (PPh ₃ ) ₄ (0.05 mmol), K ₂ CO ₃ , And stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain the product.

Product  1-1 Example of synthesis

9-chloro-4- (4,6- diphenylnaphthalen-1-yl) -7,7-dimethyl-7 H -benzo [c] fluorine (13.55 g, 24.3 mmol) was dissolved in Toluene, 4,4,5 , 5-tetramethyl-2-phenyl -1,3,2-dioxaborolane (5.46 g, 26.8 mmol), Pd (PPh 3) 4 (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.26 g (yield: 71%) of the product.

Product  1-16 Example of synthesis

9-chloro-4- (4,6- diphenylnaphthalen-1-yl) -7,7-diphenyl-7 H -benzo [c] fluorene (10.31 g, 15.1 mmol) was dissolved in Toluene, 9- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan -2-yl) phenyl) -9 H -carbazole (6.14 g, 16.6 mmol), Pd (PPh 3) 4 (0.05 mmol), K ₂ CO ₃ (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.44 g (yield: 70%) of the product.

Product  1-30 Example of synthesis

9-chloro-4- (4,6- diphenylnaphthalen-1-yl) spiro [benzo [c] fluorene-7,9'-fluorene] (10.17 g, 15.0 mmol) was dissolved in Toluene, 2- (9, 9-diphenyl-9 H -fluoren- 2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.32 g, 16.5 mmol), Pd (PPh 3) 4 (0.05 mmol), K ₂ CO ₃ (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 11.26 g (yield: 78%) of the product.

Product  2-6 Example of synthesis method

The 2- (4- (10- (9- chloro-7,7-dimethyl-7 H -benzo [c] fluoren-4-yl) anthracen-9-yl) phenyl) pyridine (10.86 g, 17.9 mmol) Toluene was dissolved in, 4,4,5,5-tetramethyl-2-phenyl -1,3,2-dioxaborolane (4.01 g, 19.7 mmol), Pd (PPh 3) 4 (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.09 g (yield: 87%) of the product.

Product  2-35 Example of synthesis method

9-chloro-4- (2,6- dimethyl-10- (naphthalen-2-yl) anthracen-9-yl) -7,7-diphenyl-7 H -benzo [c] fluorene (9.98 g, 13.6 mmol) 4,7,5,5-tetramethyl-1,3,2-dioxaborolane (4.73 g, 15.0 mmol), Pd (PPh ₃ ) _{4 (0.05 mmol), K 2} CO 3 (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.12 g (yield: 84%) of the product.

Product  2-49 Example of synthesis method

Benzo [ c ] fluorene-7,9'-fluorene] (13.71 g, 21.0 mmol) was dissolved in toluene and then 3- (4,4,4- 5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl) pyridine (4.73 g, 23.1 mmol), Pd (PPh 3) 4 (0.05 mmol), K 2 CO 3 (3 equiv), water was added And then stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.05 g (yield: 69%) of the product.

Product  3-3 Example of synthesis

4 - ([2,1 ': 3 ', 2 '' - ternaphthalen] -4'-yl) -9-chloro-7,7-dimethyl-7 H -benzo [c] fluorene (8.94 g, 13.6 mmol) Bis (tri-methylsilane) (5.21 g, 15.0 mmol) was dissolved in toluene and then a solution of (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- _{mmol), Pd (PPh 3)} 4 (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.37 g (yield: 82%) of the product.

Product  3-11 Example of synthesis

4 - ([2,1 ': 3 ', 2 '' - ternaphthalen] -4'-yl) -9-chloro-7,7-diphenyl-7 H -benzo [c] fluorene (8.68 g, 11.1 mmol) It was dissolved in Toluene, 4,4,5,5-tetramethyl-2- ( pyren-1-yl) -1,3,2-dioxaborolane (4.01 g, 12.2 mmol), Pd (PPh 3) 4 (0.05 mmol ), K ₂ CO ₃ (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.03 g (yield: 76%) of the product.

Product  3-23 Example of synthesis

2- (3- (1- (9- chlorospiro [benzo [c] fluorene-7,9'-fluoren] -4-yl) - [2,2'-binaphthalen] -4-yl) phenyl) -1- phenyl-1 H- benzo [ d ] imidazole (9.82 g, 10.7 mmol) was dissolved in toluene and then 4,4,5,5-tetramethyl-2- (naphthalen-1-yl) -1,3,2-dioxaborolane (2.98 g, 11.7 mmol), Pd (PPh 3) 4 (0.05 mmol), K 2 CO 3 (3 eq.), Water was added, and the mixture was stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.69 g (yield: 89%) of the product.

The results of performing the mass spectrometry (HRMS) on the above Compounds 1-1 to 3-32 were as shown in Table 3 below.

Meanwhile, although each of the substituents of the compounds represented by the formulas (1) to (4) is broadly related, examples of synthesis of representative compounds have been exemplarily described, but the compounds not exemplarily illustrated in the synthesis examples are also included in the present specification .

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 a substituent used in a hole injecting layer material, a hole transporting layer material, a light emitting layer material, and an electron transporting layer material used in the production of an organic electronic device including the organic light emitting device into the above structure, Materials can be prepared.

The compounds according to the present invention can be used in various applications in organic electroluminescent devices depending on the kind and nature of substituent groups.

Since the compounds of the present invention are controllable by the core and the substituent, they can act as various layers other than phosphorescent or fluorescent light emitting host hosts.

The organic electroluminescent device of the present invention can be manufactured by a conventional method and material for producing an organic electroluminescent device, except that the above-described compounds are used to form one or more organic substance layers.

It is obvious that the same effects can be obtained even when the compounds of the present invention are used for other organic layers of an organic electroluminescent device, for example, a hole transporting layer, a hole injecting layer, an electron injecting layer electron transporting layer and a light emitting auxiliary layer.

Meanwhile, the compound of the present invention can be used in a soluble process. That is, the organic compound layer of the organic electronic device described later can be formed by a soluble process of the compound. That is, when the compound is used as an organic material layer, the organic material layer may be formed by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Lt; RTI ID = 0.0 > a < / RTI > fewer layers.

Organic electronic devices in which the compounds of the invention may be used include, for example, display devices, organic electroluminescent devices (OLEDs), organic solar cells, organophotoreceptor (OPC) drums, organic transistors Devices.

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

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of the present invention to provide.

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

The organic electroluminescent device according to another embodiment of the present invention can be manufactured by the same method as the organic electroluminescent device except that at least one layer of the organic compound layer including the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, Can be made with a structure known in the art using conventional manufacturing methods and materials in the art.

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

1 to 6, the organic electroluminescent device includes a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, and at least one layer of the organic layers excluding the light emitting layer may be omitted.

The organic electroluminescent device has a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for blocking the movement of electrons, a luminescent auxiliary layer for assisting or assisting luminescence and a protective layer It may be located. In the case of the protective layer, it may be formed to protect the organic layer at the uppermost layer or to protect the cathode.

At this time, the compound of the present invention may be included in at least one of organic compound layers including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Specifically, the compound of the present invention may be used as a substitute for one or more of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, May be used. Of course, it can be used for more than two layers, not only one layer of the organic material layer.

In particular, it can be used as a hole injecting material, a hole transporting material, an electron injecting material, an electron transporting material, a light emitting material and a passivation (keping) material according to the compound of the present invention, It can be used as a dopant, and can be used as a hole injecting and hole transporting layer.

For example, the organic electroluminescent device according to another embodiment of the present invention may be formed by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, Oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer on the anode, depositing a material usable as a cathode thereon .

In addition to such a method, the organic material may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic material layer may be formed by using a variety of polymer materials, not by vapor deposition, but by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be manufactured in a small number of layers.

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

The substrate may be a silicon wafer, a quartz or glass plate, a metal plate, a plastic film, or a sheet.

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

A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent.

As the hole injecting material, a hole can be injected from the anode at a low voltage. The highest occupied molecular orbital (HOMO) of the hole injecting material may be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to an organic light emitting layer disposed thereon, and has high hole mobility, stability to holes, and electrons. In addition to these general requirements, heat resistance to a device is required when it is applied for vehicle display, and it may be a material having a glass transition temperature (Tg) of 70 DEG C or more.

Materials satisfying such conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone-based arylamine compounds, and the like.

An organic light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. The light emitting material may be a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.

Materials or compounds that satisfy these conditions include Alq3 in the case of green, Balq (8-hydroxyquinoline beryllium salt) in the case of blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) biphenyl series, Spiro material, Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenolithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complexes, imidazoles, thiazole and oxazole metal complexes, and perylene and BczVBi (3,3 ' (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine). In the case of red, the green luminescent material was doped with DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile).

Polymers such as a polyphenylene vinylene (PPV) -based polymer and polyfluorene may be used for the organic light emitting layer when the light emitting layer is formed using processes such as inkjet printing, roll coating and spin coating .

An electron transporting layer is disposed on the organic light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons.

Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq3; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

An electron injection layer is deposited on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P, boron compounds, and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ANGSTROM to 300 ANGSTROM.

On the electron injection layer, a cathode is positioned. These cathodes serve to inject electrons. The material used for the cathode may be the material used for the anode and may be a metal having a low work function for efficient electron injection. Particularly suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or their alloys may be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.

As described above, the compound of the present invention can be used as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are suitable for the fluorescence of all colors such as red, green, It can be used as a host or dopant material of various colors.

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

Meanwhile, the present invention includes a display device including the above-described organic electronic device 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 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, and various computers.

Evaluation of manufacturing of organic electric device

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting layer material. First, a hole injection layer (hole injection layer material: 4,4'4 "-tris [2-naphthyl (phenyl) amino] -triphenylamine (2-TNATA ), A hole transport layer (hole transport layer material: N ⁴ , N ^{4 '} -di (naphthalene-1-yl) -N ⁴ , N ^4' -diphenylbiphenyl-4,4'- diamine (NPB) (BD-052X is a blue fluorescent dopant, a compound of the present invention as a luminescent host material) and an electron transport layer (thickness: 250 Å) having a thickness of 250 Å electron transport layer material: tris (8-quinolinolato) aluminum (Alq _3)), an electron injection layer of 10Å thickness (electron injection layer material: lithium fluoride (LiF)) and 1500Å was sequentially deposited on an aluminum anode with a thickness of the organic An electroluminescent device was fabricated.

For comparison, an organic electroluminescent device having the same structure as that of the test example was fabricated by using Comparative Example (1) (represented by ADN) and Comparative Example (2) represented by the following formula instead of the compound of the present invention as a light emitting layer material .

Comparative Example (1) Comparative Example (2)

Electroluminescence (EL) characteristics were measured by PR-650 of a photoresearch company by applying a forward bias DC voltage to the organic electroluminescent devices thus manufactured and the comparative organic electroluminescent devices. The measurement results showed that at a luminance of 300 cd / m 2 The T90 lifetime was measured using a life-time instrument manufactured by McAfee.

Table 4 below shows device fabrication and evaluation results for Examples and Comparative Examples to which the compounds according to the invention were applied.

Compound A of the following Table 4 is a compound 9,10-di (naphthalen-3-yl) anthracene of Comparative Example 1 and Compound B is 7,7-dimethyl-5- (10-phenylanthracene -9-yl) -7H-benzo [c] fluorene.

As can be seen from the results of Table 4, the organic electroluminescent device using the material for an organic electroluminescent device of the present invention was used as a material for a light emitting layer, so that the color filter of Comparative Example 1 (ADN) Can be remarkably improved. In other words, the compound having benzofluorene improved the efficiency and lifetime more than the comparative example (1), and the substituent was introduced at the 5-position of the benzofluorene, rather than the comparative example (2) Can be seen to improve the efficiency and lifetime of the compound of the present invention. This is because the substitution of the bulky substituent at the position 4 of the benzofluorene is easier than the substitution of the benzofluorene at the position 5 of the benzofluorene, and the bulky substituent makes amorphous formation and light emission in the short wavelength region while making the structure more distorted structurally .

The compound according to the present invention can be applied not only to organic electroluminescent devices (OLEDs) but also to display devices, organic solar cells, organic photoconductors (OPC), organic transistors (organic TFT), monochromatic or white illumination devices Can also be used.

It is apparent that the same effects can be obtained even when the compounds of the present invention are used in other organic layers of an organic electroluminescent device, for example, a light emitting layer, a light emitting auxiliary layer, an electron injecting layer and an electron transporting 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 is 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)

A compound for an organic electroluminescent device comprising a compound represented by the following formula (3).
(3)

In Formula 3,
(1) Ar ₁ is hydrogen, deuterium, tritium, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C of ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group , A C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group, An unsubstituted C ₆ to C ₆₀ aryl group ;
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and is unsubstituted or substituted with a substituent selected from the group consisting of acetylene, O, N, S, Si , C 2 ~ C ₆₀ heteroaryl rings containing at least one hetero atom of the group P;
A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group and C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of group; And
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 ₁ ~ C ₅₀ in the alkyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group substituted or a substituent selected from the group consisting of An unsubstituted fluorene group; , ≪ / RTI >
(2) Ar ₂ represents hydrogen, deuterium, tritium, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C of ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group , A C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group, An unsubstituted C ₆ to C ₆₀ aryl group; And
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and is unsubstituted or substituted with a substituent selected from the group consisting of acetylene, O, N, S, Si , C 2 ~ C ₆₀ heteroaryl rings containing at least one hetero atom of the group P; , ≪ / RTI >
(3) R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, tritium, a halogen group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, A C ₆ to C ₂₀ arylalkyl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group A C ₁ to C ₅₀ alkyl group substituted or unsubstituted with a selected substituent ; And
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; R ₁ and R ₂ may be bonded to each other to form a spiro compound,
(4) R ₅ is substituted with a 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 C ₆ ~ an aryl group of C _20, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, a nitrile group, and substituted with an acetylene group a substituent selected from the group consisting or unsubstituted of A C ₁ to C ₅₀ alkyl group;
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and A C ₂ to C ₆₀ heterocyclic group which is substituted or unsubstituted with a substituent selected from the group consisting of an acetylene group and at least one heteroatom selected from O, N, S, Si and P ;
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ of the arylamine group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ heterocyclic group of C ₂₀ arylalkyl groups, C ₈ ~ C ₂₀ arylalkenyl group, C ₂ ~ C ₂₀ of the nitrile group and A C ₂ ~C ₂₀ alkenyl group substituted or unsubstituted with a substituent in 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, Substituted or unsubstituted C ₁ -C ₃₀ alkyl group substituted or unsubstituted with a substituent selected from the group consisting of a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C ₂₀ arylalkenyl group, a C ₂ -C ₂₀ heterocyclic group, a nitrile group and an acetylene group, An alkoxy group ;
A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₃ to C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of 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 substituted or unsubstituted aryl groups substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl groups, C ₈ -C ₂₀ arylalkenyl groups, C ₂ -C ₂₀ heterocyclic groups, nitrile groups and acetylene groups, An aryloxy group; And
Hydrogen, deuterium, tritium, a halogen group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a substituted C by deuterium 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 ; , ≪ / RTI >
(5) n is an integer of 1 or 2,
(6) Each of R ₁ and R ₂ , Ar ₁ and Ar ₂ may be bonded to or react with an adjacent group to form a substituted or unsubstituted saturated or unsaturated ring. The method according to claim 1,
Wherein each of R ₁ and R ₂ , Ar ₁ and Ar ₂ is bonded to or reacted with adjacent groups to form a saturated or unsaturated ring. delete The method according to claim 1,
A compound for an organic electroluminescent device, characterized in that it is one of the following compounds.

An organic electroluminescent device comprising at least one organic layer comprising the compound of claim 1 or 2. 6. The method of claim 5,
Wherein said compound is formed into said organic material layer by a solution process. 6. The method of claim 5,
An organic electroluminescent device comprising a first electrode sequentially laminated, an organic material layer and a second electrode 6. The method of claim 5,
Wherein the organic material layer comprises at least one of a light emitting layer, a hole injecting layer, a hole transporting layer, an electron injecting layer, and an electron transporting layer. The method of claim 8, wherein
Wherein the compound is used as the light emitting layer material. A display device comprising the organic electroluminescent device of claim 5; And
And a control unit for driving the display device. The method of claim 10, wherein
Wherein 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), and a monochromatic or white illumination device.

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