KR101292554B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

PURPOSE: A compound is provided to obtain high light emitting efficiency, low driving voltage, and high heat resistance, and to remarkably improve the color purity and the lifetime of a diode. CONSTITUTION: A compound for an organic electroluminescent diode is represented by chemical formula 2-5. In the chemical formulas, each of R4 and R5 is a C6-C25 aryl group substituted or non-substituted by a substituted which is selected from hydrogen, a C1-C4 alkyl group, a C2-C6 alkenyl group, and a C6-C20 aryl group; or a C2-C20 alkenyl group substituted or non-substituted by a substituent which is selected from hydrogen, a C1-C4 alkyl group, a C2-C6 alkenyl group, and C6-C20 aryl group; or R4 and R5 are a substituted or non non-substituted saturated or unsaturated ring by being coupled with each other; and each of a and b is an integer from 1-5.

Description

COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF

The present invention relates to a compound, an organic electric element comprising the same, and an electronic device thereof.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. 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.

On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. 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.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

It is an object of the present invention to provide a compound capable of improving a high luminous efficiency, a low driving voltage, a high heat resistance, a color purity and a lifetime of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the invention provides compounds represented by the formula:

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

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

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

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are 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."

The term " halo "or" halogen "as used herein, on the other hand, includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

The term "alkyl" or "alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxy group" as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used in the present invention, each have 6 to 60 carbon atoms, but are not limited thereto.

In the present invention, an aryl group or an arylene group means an aromatic group having a single ring or a heterocyclic ring, and the neighboring substituent includes an aromatic ring 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 "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 3 to 60 carbon atoms each containing at least one heteroatom, But includes a single ring as well as a heterocyclic ring and may be formed by bonding adjacent groups.

The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

As used herein, the term “heteroatom” refers to N, O, S, P, and Si unless otherwise indicated.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise indicated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or hetero ring having 6 to 60 carbon atoms.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention alkoxy group, C ₁ ~ C ₂₀ alkyl amine group of _20, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron of Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Having an organic compound layer containing a compound represented by the general formula (1). In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer can be formed using a variety of polymer materials by a solution process other than a vapor deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be made of a number of layers. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

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.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by the following formula (1).

In Formula 1, R ₁ , R ₂ are each independently hydrogen; heavy hydrogen; Tritium; Halogen 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 arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ An alkyl group; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of acetylene groups and containing at least one heteroatom of O, N, S, Si and P ; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with one or more substituents selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl; 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 Selected from the group consisting of ₆ to C ₂₀ aryl groups, C ₆ to C ₂₀ arylamine groups, C ₈ to C ₂₀ arylalkenyl groups, silane groups, boron groups, germanium groups and C ₂ to C ₂₀ heterocyclic groups aryl groups substituted or unsubstituted with one or more substituents of C ₆ ~ C ₆₀ ring which; And C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group and C ₂ ~ C ₂₀ by at least one substituent selected from the heterocyclic group ring group consisting of a substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group; ≪ / RTI >

In addition, in Formula 1, m is an integer of 1 to 2; n is an integer of 1 to 4; When m and n are integers of 2 or more, each of R ₁ and R ₂ may be the same or different from each other, and R ₁ and R ₂ may be bonded to each other or with adjacent groups to form an alicyclic or aromatic monocyclic or polycyclic ring. can do.

In Formula 1, L is nitro, nitrile, halogen, C ₁ ~ C ₂₀ Alkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ Aryl group, C ₂ ~ C ₂₀ Heterocyclic group and amino group substituted with one or more substituents selected from the group consisting of and unsubstituted C ₆ ~ C ₆₀ arylene group; Hydrogen, deuterium, tritium, halogen, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C A fluorenylene group unsubstituted or substituted with a substituent selected from the group consisting of ₂₀ arylalkenyl groups, C ₁ to C ₅₀ alkyl groups, C ₂ to C ₂₀ heterocyclic groups, nitrile groups and acetylene groups ; _{One 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 C ₃ ~ C ₆₀ hetero arylene group unsubstituted or substituted with the above substituents ; And divalent substituted or unsubstituted aliphatic hydrocarbons; ≪ / RTI >

In addition, in Formula 1, Ar ₁ and Ar ₂ is hydrogen, deuterium, tritium, halogen, 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 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, of a C ₆ ~ C ₂₀ aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, C ₆ ~ C ₂₀ substituted by deuterium aryl amine group, a silane group, a boron group, a germanium group, phosphine oxide group and an aryl group of C ₂ ~ C ₂₀ by at least one substituent selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₆₀ of; 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 A C ₂ to C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more substituents in the group consisting of acetylene groups and comprises at least one heteroatom of O, N, S, Si and 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 substituted from the group consisting of acetylene with one or more substituents or unsubstituted alkenyl group of C ₂ ~ C _20; And hydrogen, deuterium, tritium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium 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 fluorene group; ≪ / RTI >

On the other hand, Formula 1 may be represented by any one of the following formula (2) to formula (5).

In Formulas (2) to (5), R ₄ , R ₅ are An aryl group of hydrogen, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₆ alkenyl group and a C ₆ ~ C ₂₀ aryl unsubstituted or substituted with a substituent selected from the group consisting of a C ₆ ~ C ₂₅ of the; Or hydrogen, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₆ alkenyl group, C ₆ ~ C ₂₀ aryl unsubstituted or substituted with a substituent selected from the group consisting of a C ₂ ~ C ₂₀ of the alkenyl group; R ₄ and R ₅ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, and a and b each represent an integer of 1 to 5, respectively.

In addition, the formulas (2) to (5) may be used as a light emitting auxiliary layer of the organic material layer used in the organic light emitting device.

More specifically, the compound represented by Formula 1 may be one of the following compounds P-1 to P-63.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Compounds (final products) according to the present invention is prepared by the reaction of Sub 1 and Sub 4, as shown in Scheme 1.

<Reaction Scheme 1>

Sub  Synthesis of 1

Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2 below.

<Reaction Scheme 2>

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

(One) Sub  1-1 Synthetic example

<Reaction Scheme 3>

Starting material 1 H -indole (57.12 g, 487.6 mmol) was dissolved in nitrobenzene in a round bottom flask, Sub 1-I-1 (245.06 g, 682.6 mmol), Na ₂ SO ₄ (69.24 g, 487.6 mmol), K ₂ CO ₃ (67.29 g, 487.6 mmol), Cu (9.3 g, 146.3 mmol) was added and stirred at 200 ° C. When the reaction was complete, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give 120.56 g (yield: 71%) of the product.

(2) Sub  1-3 Synthetic example

<Reaction Scheme 4>

In the starting material 5-phenyl-1 H -indole (50.82 g, 263 mmol), Sub 1-I-1 (132.18 g, 368.2 mmol), Na ₂ SO ₄ (37.35 g, 263 mmol), K ₂ CO ₃ ( 36.29 g, 263 mmol), Cu (5.01 g, 78.9 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 75.89 g (yield: 68%) of the product.

(3) Sub  1-5 Synthetic example

Scheme 5

2-phenyl-1 H -indole (51.97 g, 268.9 mmol) as a starting material, Sub 1-I-1 (135.15 g, 376.5 mmol), Na ₂ SO ₄ (38.18 g, 268.9 mmol), K ₂ CO ₃ (37.11 g, 268.9 mmol), Cu (5.13 g, 80.7 mmol), nitrobenzene were obtained using the Sub 1-1 synthesis of Example 1 above. 71.88 g of the product (yield: 63%).

(4) Sub  1-7 Synthetic example

<Reaction Scheme 6>

Starting material 2,3-diphenyl-1 H -indole (61.54 g, 228.5 mmol) in Sub 1-I-1 (114.83 g, 319.9 mmol), Na ₂ SO ₄ (32.45 g, 228.5 mmol), K ₂ CO ₃ (31.53 g, 228.5 mmol), Cu (4.36 g, 68.6 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 67.47 g (yield: 59%) of the product.

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

Examples of Sub 1 include, but are not limited to, the following, and their FD-MSs are shown in Table 1 below.

compound FD-MS compound FD-MS Sub 1-1 m / z = 347.03 (C ₂₀ H ₁₄ BrN = 348.24) Sub 1-2 m / z = 365.02 (C ₂₀ H ₁₃ BrFN = 366.23) Sub 1-3 m / z = 423.06 (C ₂₆ H ₁₈ BrN = 424.33) Sub 1-4 m / z = 424.06 (C ₂₅ H ₁₇ BrN ₂ = 425.32) Sub 1-5 m / z = 423.06 (C ₂₆ H ₁₈ BrN = 424.33) Sub 1-6 m / z = 514.10 (C ₃₂ H ₂₃ BrN ₂ = 515.44) Sub 1-7 m / z = 499.09 (C ₃₂ H ₂₂ BrN = 500.43)

Sub  Synthesis of 4

Sub 4 of Scheme 1 may be synthesized by the reaction route of Scheme 7.

<Reaction Scheme 7>

Synthesis examples of specific compounds belonging to Sub 4 are as follows.

(One) Sub  4-1 Synthetic example

<Reaction Scheme 8>

After starting bromobenzene (42.85 g, 272.9 mmol) was dissolved in toluene in a round bottom flask, aniline (50.83 g, 545.8 mmol), Pd ₂ (dba) ₃ (7.5 g, 8.2 mmol), 50% P ( t- Bu) ₃ (8 ml, 16.4 mmol), NaO t -Bu (78.69 g, 818.7 mmol) was added and stirred at 40 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 31.86 g (yield: 69%) of the product.

(2) Sub  4-7 Synthetic example

<Reaction Scheme 9>

Bromobenzene (24.18 g, 154.3 mmol) obtained in the above synthesis was naphthalen-2-amine (44.18 g, 308.6 mmol), Pd ₂ (dba) ₃ (4.24 g, 4.63 mmol), 50% P ( t -Bu) ₃ ( 4.5 ml, 9.26 mmol), NaO t -Bu (44.49 g, 462.9 mmol) and toluene were obtained using the Sub 4-1 synthesis of Example 4 above to obtain 27.69 g (yield: 82%) of the product.

(3) Sub  4-13 Synthetic example

<Reaction formula 10>

[1,1'-biphenyl] -4-amine (74.71 g, 441.5 mmol), Pd ₂ (dba) ₃ (6.06) to 4-bromo-1,1'-biphenyl (51.46 g, 220.7 mmol) obtained in the above synthesis. g, 6.6 mmol), 50% P ( t -Bu) ₃ (6.5ml, 13.2 mmol), NaO t -Bu (63.63 g, 662.1 mmol) and toluene were synthesized using the Sub 4-1 synthesis of Example 4 above. 56.75 g (yield: 80%) of the product were obtained.

(4) Sub  4-16 Synthetic example

<Reaction Scheme 11>

To 4-bromo-1,1 ': 3', 1 ''-terphenyl (47.33 g, 153.1 mmol) obtained in the above synthesis, aniline (28.51 g, 306.1 mmol), Pd ₂ (dba) ₃ (4.2 g, 4.6 mmol ), 50% P ( t -Bu) ₃ (4.5 ml, 9.2 mmol), NaO t -Bu (44.13 g, 459.2 mmol), toluene were obtained using 37.89 g of the product using the Sub 4-1 synthesis of Example 4. Yield: 77%).

(5) Sub  4-22 Synthetic example

<Reaction Scheme 12>

To 2-bromo-9,9-dimethyl-9 H -fluorene (40.24 g, 147 mmol) obtained in the above synthesis, [1,1'-biphenyl] -4-amine (49.86 g, 295 mmol), Pd ₂ (dba ) ₃ (4.04 g, 4.4 mmol), 50% P ( t -Bu) ₃ (4.3ml, 8.8 mmol), NaO t -Bu (42.38 g, 441 mmol), toluene were obtained according to the Sub 4-1 of Example 4. Synthesis gave 38.26 g (yield: 72%) of product.

(6) Sub  4-26 Synthetic example

<Reaction Scheme 13>

To 2-bromo-9,9-diphenyl-9 H -fluorene (38.93 g, 98 mmol) obtained in the above synthesis, [1,1'-biphenyl] -4-amine (33.16 g, 196 mmol), Pd ₂ (dba ) ₃ (2.66 g, 2.9 mmol), 50% P ( t -Bu) ₃ (2.9ml, 5.9 mmol), NaO t -Bu (28.26 g, 294 mmol), toluene Synthesis gave 32.36 g (yield: 68%) of product.

Meanwhile, examples of Sub 4 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 2 below.

compound FD-MS compound FD-MS Sub 4-1 m / z = 169.09 (C ₁₂ H ₁₁ N = 169.22) Sub 4-2 m / z = 209.12 (C ₁₅ H ₁₅ N = 209.29) Sub 4-3 m / z = 249.15 (C ₁₈ H ₁₉ N = 249.35) Sub 4-4 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 4-5 m / z = 259.14 (C ₁₉ H ₁₇ N = 259.34) Sub 4-6 m / z = 295.14 (C ₂₂ H ₁₇ N = 295.38) Sub 4-7 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 4-8 m / z = 259.14 (C ₁₉ H ₁₇ N = 259.34) Sub 4-9 m / z = 295.14 (C ₂₂ H ₁₇ N = 295.38) Sub 4-10 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 4-11 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 4-12 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 4-13 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 4-14 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 4-15 m / z = 285.15 (C ₂₁ H ₁₉ N = 285.38) Sub 4-16 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 4-17 m / z = 397.18 (C ₃₀ H ₂₃ N = 397.51) Sub 4-18 m / z = 335.17 (C ₂₅ H ₂₁ N = 335.44) Sub 4-19 m / z = 335.17 (C ₂₅ H ₂₁ N = 335.44) Sub 4-20 m / z = 325.18 (C ₂₄ H ₂₃ N = 325.45) Sub 4-21 m / z = 285.15 (C ₂₁ H ₁₉ N = 285.38) Sub 4-22 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.48) Sub 4-23 m / z = 401.21 (C ₃₀ H ₂₇ N = 401.54) Sub 4-24 m / z = 409.18 (C ₃₁ H ₂₃ N = 409.52) Sub 4-25 m / z = 459.20 (C ₃₅ H ₂₅ N = 459.58) Sub 4-26 m / z = 485.21 (C ₃₇ H ₂₇ N = 485.62) Sub 4-27 m / z = 407.17 (C ₃₁ H ₂₁ N = 407.51) Sub 4-28 m / z = 483.20 (C ₃₇ H ₂₅ N = 483.60)

Product Synthesis of

Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 1 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.

(One) Product  P-1 Synthetic example

<Reaction Scheme 14>

Sub 4-22 (7.5 g, 20.8 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 1-5 (10.57 g, 24.9 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.6 mmol) , 50% P ( t- Bu) ₃ (0.8 ml, 1.7 mmol), NaO t -Bu (6 g, 62.4 mmol) was added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 11.88 g (yield: 81%).

(2) Product  P-2 Synthetic example

<Reaction Scheme 15>

To Sub 4-13 (7.71 g, 24 mmol) obtained in the above synthesis Sub 1-5 (12.22 g, 28.8 mmol), Pd ₂ (dba) ₃ (0.64 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.9 mmol), NaO t -Bu (6.92 g, 72 mmol), toluene were obtained using 11.81 g (yield: 74%) of the product using the Product P-1 synthesis method of Example 3.

(3) Product  P-4 Synthetic example

<Reaction Scheme 16>

Sub 4-13 (7.29 g, 22.7 mmol) obtained in the above synthesis in Sub 1-7 (13.62 g, 27.2 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.8 mmol), NaO t -Bu (6.55 g, 68.1 mmol) and toluene were obtained using the Product P-1 synthesis method of Example 3, to obtain 12.11 g (yield: 72%).

(4) Product  P-5 Synthetic example

<Reaction Scheme 17>

Sub 4-22 (8.21 g, 22.7 mmol) obtained in the above synthesis in Sub 1-3 (11.58 g, 27.3 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.8 mmol), NaO t -Bu (6.55 g, 68.1 mmol) and toluene were obtained using the Product P-1 synthesis method of Example 3 (12 g, yield: 75%).

(5) Product  P-6 Synthetic example

<Reaction Scheme 18>

Sub 4-13 (10.37 g, 32.3 mmol) obtained in the above synthesis to Sub 1-3 (16.43 g, 38.7 mmol), Pd ₂ (dba) ₃ (0.89 g, 1 mmol), 50% P ( t -Bu) ₃ (1.3 ml, 2.6 mmol), NaO t -Bu (9.31 g, 96.3 mmol) and toluene were obtained using the Product P-1 synthesis method of Example 3 to obtain 17.6 g (yield: 82%) of the product.

On the other hand, FD-MS values of the compounds P-1 ~ P-12, P-21 ~ P-63 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

compound FD-MS compound FD-MS P-1 m / z = 704.32 (C ₅₃ H ₄₀ N ₂ = 704.90) P-2 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) P-3 m / z = 740.32 (C ₅₆ H ₄₀ N ₂ = 740.93) P-4 m / z = 740.32 (C ₅₆ H ₄₀ N ₂ = 740.93) P-5 m / z = 704.32 (C ₅₃ H ₄₀ N ₂ = 704.90) P-6 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) P-7 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) P-8 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) P-9 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P-10 m / z = 750.30 (C ₅₇ H ₃₈ N ₂ = 750.93) P-11 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P-12 m / z = 674.27 (C ₅₁ H ₃₄ N ₂ = 674.83) P-21 m / z = 436.19 (C ₃₂ H ₂₄ N ₂ = 436.55) P-22 m / z = 486.21 (C ₃₆ H ₂₆ N ₂ = 486.61) P-23 m / z = 486.21 (C ₃₆ H ₂₆ N ₂ = 486.61) P-24 m / z = 512.23 C ₃₈ H ₂₈ N ₂ = 512.64) P-25 m / z = 552.26 (C ₄₁ H ₃₂ N ₂ = 552.71) P-26 m / z = 476.23 (C ₃₅ H ₂₈ N ₂ = 476.61) P-27 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P-28 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P-29 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) P-30 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) P-31 m / z = 526.24 (C ₃₉ H ₃₀ N ₂ = 526.67) P-32 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P-33 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) P-34 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) P-35 m / z = 526.24 (C ₃₉ H ₃₀ N ₂ = 526.67) P-36 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) P-37 m / z = 628.29 (C ₄₇ H ₃₆ N ₂ = 628.80) P-38 m / z = 552.26 (C ₄₁ H ₃₂ N ₂ = 552.71) P-39 m / z = 668.32 (C ₅₀ H ₄₀ N ₂ = 668.87) P-40 m / z = 592.29 (C ₄₄ H ₃₆ N ₂ = 592.77) P-41 m / z = 516.26 (C ₃₈ H ₃₂ N ₂ = 516.67) P-42 m / z = 454.18 (C ₃₂ H ₂₃ FN ₂ = 454.54) P-43 m / z = 512.23 (C ₃₈ H ₂₈ N ₂ = 512.64) P-44 m / z = 603.27 (C ₄₄ H ₃₃ N ₃ = 603.75) P-45 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P-46 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) P-47 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P-48 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) P-49 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P-50 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P-51 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) P-52 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) P-53 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P-54 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) P-55 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P-56 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P-57 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P-58 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) P-59 m / z = 780.35 (C ₅₉ H ₄₄ N ₂ = 780.99) P-60 m / z = 904.38 (C ₆₉ H ₄₈ N ₂ = 905.13) P-61 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P-62 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P-63 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96)

On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), these are all based on the Suzuki cross-coupling reaction, Ullmann reaction and Buchwald-Hartwig cross coupling reaction and the like in addition to the substituents specified in the specific synthesis examples Those skilled in the art will readily understand that the reaction proceeds even if other defined substituents (substituents such as R ₁ , R ₂ , L, Ar ₁ , Ar _2, etc.) are combined. For example, the starting material-> Sub 1 reaction in Scheme 2 is based on the Ullmann reaction, and the starting material-> Sub 4, Product synthetic reaction in Scheme 7 (Scheme 14 to Scheme 18) is based on the Buchwald-Hartwig cross coupling reaction. The reactions will proceed even if the substituents are not specified.

Evaluation of manufacturing of organic electric device

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the organic substrate to form a hole injection layer having a thickness of 60 nm, the hole transport layer was formed by vacuum depositing the compound according to the present invention to a thickness of 20 nm on the hole injection layer. Formed. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as the host material on the hole transport layer and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] is used as the dopant material. Doped at a weight ratio to deposit a light emitting layer to a thickness of 30nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm with a holding layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was formed into a transport layer to a thickness of 40 nm. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic light emitting device.

[ Comparative example  One]

An organic light emitting diode was manufactured in the same manner as in Example 4, except that Comparative Compound 1 was used instead of the compound according to the present invention as a material for the hole transport layer.

           <Comparative Compound 1>

[ Comparative example  2]

An organic light emitting device was manufactured in the same manner as in Example 4, except that Comparative Compound 2 was used instead of the compound according to the present invention as a material for the hole transport layer.

         &Lt; Comparative Compound 2 >

As a result of measuring the characteristics of the electroluminescent device by applying a forward bias DC voltage to the organic electroluminescent device manufactured by Example 4, Comparative Example 1 and Comparative Example 2 as described above by PR-650 of photoresearch company Table 4 is as follows. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Voltage
(V) Current Density (mA / cm2) Brightness
(cd / m &lt; 2 & Efficiency
(cd / A) Lifetime
T (90) CIE x y Comparative Example (1) Comparative compound 1 5.5 6.3 300.0 4.8 68.6 0.32 0.61 Comparative Example (2) Comparative compound 2 5.8 6.5 300.0 4.5 60.9 0.32 0.62 Example (1) Compound (P-1) 4.6 4.9 300.0 6.2 114.0 0.32 0.61 Example (2) Compound (P-2) 4.7 4.8 300.0 6.2 114.7 0.32 0.61 Example (3) Compound (P-3) 4.8 5.2 300.0 5.7 105.8 0.32 0.61 Example (4) Compound (P-4) 4.5 4.6 300.0 6.5 125.9 0.32 0.62 Example (5) Compound (P-5) 4.2 4.2 300.0 7.2 138.2 0.32 0.61 Example (6) Compound (P-6) 4.3 4.2 300.0 7.2 139.9 0.32 0.61 Example (7) Compound (P-7) 4.6 4.6 300.0 6.5 117.0 0.32 0.62 Example (8) Compound (P-8) 4.4 4.7 300.0 6.4 121.3 0.32 0.61 Example (9) Compound (P-9) 5.2 5.3 300.0 5.7 91.4 0.32 0.61 Example (10) Compound (P-10) 5.2 5.7 300.0 5.3 80.8 0.32 0.62 Example (11) Compound (P-11) 5.3 5.5 300.0 5.4 83.3 0.32 0.61 Example (12) Compound (P-12) 5.3 5.7 300.0 5.3 89.6 0.32 0.61 Example (13) Compound (P-21) 5.3 5.6 300.0 5.3 78.2 0.32 0.61 Example (14) Compound (P-22) 5.2 5.8 300.0 5.2 72.3 0.32 0.62 Example (15) Compound (P-23) 5.3 5.6 300.0 5.3 79.0 0.32 0.62 Example (16) Compound (P-24) 5.3 5.6 300.0 5.4 89.2 0.32 0.61 Example (17) Compound (P-25) 5.3 5.6 300.0 5.3 75.8 0.32 0.61 Example (18) Compound (P-26) 5.3 5.9 300.0 5.1 74.2 0.32 0.61 Example (19) Compound (P-27) 5.2 5.6 300.0 5.3 85.3 0.32 0.61 Example (20) Compound (P-28) 5.2 5.6 300.0 5.4 72.9 0.32 0.61 Example (21) Compound (P-29) 5.2 5.7 300.0 5.2 74.6 0.32 0.62 Example (22) Compound (P-30) 5.3 5.7 300.0 5.3 79.6 0.32 0.62 Example (23) Compound (P-31) 5.3 6.1 300.0 4.9 73.6 0.32 0.62 Example (24) Compound (P-32) 5.3 5.8 300.0 5.2 85.3 0.32 0.62 Example (25) Compound (P-33) 5.3 5.7 300.0 5.3 88.7 0.32 0.61 Example (26) Compound (P-34) 5.2 5.7 300.0 5.3 84.7 0.32 0.61 Example (27) Compound (P-35) 5.4 6.1 300.0 4.9 74.6 0.32 0.62 Example (28) Compound (P-36) 5.1 5.4 300.0 5.5 97.6 0.32 0.62 Example (29) Compound (P-37) 5.2 5.4 300.0 5.5 97.5 0.32 0.62 Example (30) Compound (P-38) 5.3 6.1 300.0 4.9 73.5 0.32 0.61 Example (31) Compound (P-39) 5.2 5.8 300.0 5.1 72.5 0.32 0.62 Example (32) Compound (P-40) 5.3 6.0 300.0 5.0 74.0 0.32 0.62 Example (33) Compound (P-41) 5.3 6.0 300.0 5.0 71.2 0.32 0.61 Example (34) Compound (P-42) 5.4 5.9 300.0 5.1 73.8 0.32 0.62 Example (35) Compound (P-43) 4.4 4.7 300.0 6.4 125.2 0.32 0.62 Example (36) Compound (P-44) 5.4 6.0 300.0 5.0 73.9 0.32 0.61 Example (37) Compound (P-45) 5.3 5.7 300.0 5.2 79.5 0.32 0.62 Example (38) Compound (P-46) 4.3 4.3 300.0 6.9 135.7 0.32 0.61 Example (39) Compound (P-47) 4.4 4.7 300.0 6.4 119.4 0.32 0.61 Example (40) Compound (P-48) 4.5 4.6 300.0 6.5 116.0 0.32 0.62 Example (41) Compound (P-49) 4.5 4.6 300.0 6.5 120.0 0.32 0.61 Example (42) Compound (P-50) 4.4 4.6 300.0 6.6 126.5 0.32 0.62 Example (43) Compound (P-51) 4.9 5.1 300.0 5.9 106.6 0.32 0.61 Example (44) Compound (P-52) 4.6 4.8 300.0 6.2 113.3 0.32 0.61 Example (45) Compound (P-53) 4.7 5.1 300.0 5.9 109.2 0.32 0.61 Example (46) Compound (P-54) 4.7 4.9 300.0 6.1 106.1 0.32 0.61 Example (47) Compound (P-55) 4.9 5.0 300.0 6.0 109.6 0.32 0.61 Example (48) Compound (P-56) 4.8 5.1 300.0 5.9 104.1 0.32 0.61 Example (49) Compound (P-57) 4.6 4.8 300.0 6.3 105.1 0.32 0.61 Example (50) Compound (P-58) 4.6 4.9 300.0 6.1 112.7 0.32 0.61 Example (51) Compound (P-59) 4.4 4.7 300.0 6.4 122.2 0.32 0.61 Example (52) Compound (P-60) 4.5 4.7 300.0 6.4 122.0 0.32 0.62 Example (53) Compound (P-61) 4.8 4.8 300.0 6.3 111.4 0.32 0.62 Example (54) Compound (P-62) 4.7 5.0 300.0 6.1 108.8 0.32 0.61 Example (55) Compound (P-63) 4.6 4.9 300.0 6.1 113.7 0.32 0.62

As can be seen from the results of Table 4, the organic light emitting device using the compound according to the present invention as the material for the organic light emitting device (hole transporting material) has a lower driving voltage than the comparative example 1, Comparative Example 2, luminous efficiency Not only was this improved, but the service life was significantly improved. In other words, the main substituent connected to N of the carbazole and indole cores and the main substituent connected to the backbone of the carbazole core have the characteristics of low driving voltage, high efficiency and long life. Seemed. In particular, compounds P-5, P-6 and P-46 according to the present invention, which are indole cores substituted with a phenyl group at position 5, showed the best results.

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, 4,4-bis [N- (1-nap) as a hole transport compound on the hole injection layer Tyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Next, the compound according to the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. After forming the emission auxiliary layer, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material on the top and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) as the dopant material iridium (III) acetylacetonate] was deposited at a weight ratio of 95: 5 to deposit a light emitting layer having a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm with a holding layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a transport layer to a thickness of 40 nm. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic light emitting device.

[ Comparative example  3]

An organic light emitting diode was manufactured in the same manner as in Example 5, except that the Comparative Compound 1 was used to form the emission auxiliary layer instead of the compound according to the present invention.

[ Comparative example  4]

An organic light emitting diode was manufactured in the same manner as in Example 5, except that the Comparative Compound 2 was used to form the emission auxiliary layer instead of the compound according to the present invention.

[ Comparative example  5]

An organic light emitting diode was manufactured in the same manner as in Example 5, but the emission auxiliary layer was formed using the following Comparative Compound 3 instead of the compound according to the present invention.

          &Lt; Comparative Compound 3 >

[ Comparative example  6]

An organic light emitting diode was manufactured in the same manner as in Example 5, but the emission auxiliary layer was formed using the following Comparative Compound 4 instead of the compound according to the present invention.

        Comparative Compound 4

[ Comparative example  7]

An organic light emitting diode was manufactured in the same manner as in Example 5, but the emission auxiliary layer was formed using the following Comparative Compound 5 instead of the compound according to the present invention.

         Comparative Compound 5

[ Comparative example  8]

An organic light emitting diode was manufactured in the same manner as in Example 5, but the emission auxiliary layer was formed using the following Comparative Compound 6 instead of the compound according to the present invention.

          Comparative Compound 6

As a result of measuring the electroluminescence (EL) characteristics with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic light emitting device manufactured according to Example 5, Comparative Examples 3 to 8 as described above It is shown in Table 5 below. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Voltage
(V) Current Density (mA / cm2) Brightness
(cd / m &lt; 2 & Efficiency
(cd / A) Lifetime
T (90) CIE x y Comparative Example (3) Comparative compound 1 6.0 4.6 300.0 6.5 81.8 0.66 0.32 Comparative Example (4) Comparative compound 2 5.7 4.3 300.0 6.7 92.1 0.66 0.32 Comparative Example (5) Comparative compound 3 6.3 4.8 300.0 6.3 70.2 0.66 0.33 Comparative Example (6) Comparative Compound 4 6.3 5.1 300.0 5.9 78.9 0.66 0.32 Comparative Example (7) Comparative Compound 5 6.2 4.8 300.0 6.3 72.5 0.66 0.33 Comparative Example (8) Comparative Compound 6 6.2 4.3 300.0 6.2 74.8 0.66 0.33 Example (1) Compound (P-1) 5.4 4.0 300.0 7.6 127.3 0.66 0.33 Example (2) Compound (P-2) 5.4 4.0 300.0 7.5 128.5 0.66 0.33 Example (3) Compound (P-4) 5.4 3.9 300.0 7.8 135.4 0.66 0.32 Example (4) Compound (P-5) 5.0 3.6 300.0 8.4 162.7 0.66 0.32 Example (5) Compound (P-6) 5.0 3.6 300.0 8.3 160.6 0.66 0.32 Example (6) Compound (P-9) 5.5 4.3 300.0 6.9 109.7 0.66 0.32 Example (7) Compound (P-36) 5.6 4.4 300.0 6.9 106.8 0.66 0.32 Example (8) Compound (P-37) 5.5 4.4 300.0 6.8 112.6 0.66 0.33 Example (9) Compound (P-46) 5.2 3.8 300.0 8.0 149.4 0.66 0.32 Example (10) Compound (P-52) 5.5 4.0 300.0 7.4 127.7 0.66 0.33 Example (11) Compound (P-59) 5.4 3.8 300.0 7.9 120.6 0.66 0.32 Example (12) Compound (P-60) 5.3 3.9 300.0 7.7 136.1 0.66 0.32

In Table 4, an indole core, which exhibited low driving voltage, high efficiency, and high lifetime, was used as a red phosphorescent auxiliary layer material. Table 5 shows the following results.

When the arylamine group (compound according to the present invention) came to the main substituent than the heterocyclic group containing N (Comparative Example 5 to Comparative Example 8), the charge balance was maintained and the T1 value was lowered. Effective blocking to stay on the edges results in a significant improvement in both efficiency and lifetime. This is because the compounds according to the present invention have a high T1 energy level and a deep HOMO energy level, the holes are more smoothly transported from the hole transport layer to the light emitting layer, and the excitons are confined in the light emitting layer to prevent light leakage. Because it is possible to implement.

Focusing on the indole core, the indole core substituted with the phenyl group has improved efficiency and lifespan than the unsubstituted indole core, and especially the compound P-5 and P- of the present invention, which is an indole core substituted with a phenyl group at position 5 It can be seen that the sixth lamp is more than twice the lifespan compared to Comparative Example 3 with a low driving voltage.

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, 4,4-bis [N- (1-nap) as a hole transport compound on the hole injection layer Tyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Next, the compound according to the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. After the emission auxiliary layer was formed, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] was used as a dopant material. Doped at a weight ratio of 95: 5 to deposit a light emitting layer at a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm with a holding layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a transport layer to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting device.

[ Comparative example  9]

An organic light emitting diode was manufactured in the same manner as in Example 8, except that the Comparative Compound 1 was used to form the emission auxiliary layer instead of the compound according to the present invention.

[ Comparative example  10]

An organic light emitting diode was manufactured in the same manner as in Example 8, except that the Comparative Compound 2 was used instead of the compound according to the present invention to form a light emitting auxiliary layer.

[ Comparative example  11]

An organic light emitting diode was manufactured in the same manner as in Example 8, except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound according to the present invention.

[ Comparative example  12]

An organic light emitting diode was manufactured in the same manner as in Example 8, except that the Comparative Compound 4 was used to form the emission auxiliary layer instead of the compound according to the present invention.

[ Comparative example  13]

An organic EL device was manufactured in the same manner as in Example 8, except that the Comparative Compound 5 was used instead of the compound according to the present invention to form a light emitting auxiliary layer.

[ Comparative example  14]

An organic light emitting diode was manufactured in the same manner as in Example 8, but the emission auxiliary layer was formed using the comparative compound 6 instead of the compound according to the present invention.

As a result of measuring the electroluminescence (EL) characteristics with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic EL device manufactured in Example 8, Comparative Example 9 and Comparative Example 14 as described above It is shown in Table 6 below. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Voltage
(V) Current Density (mA / cm2) Brightness
(cd / m &lt; 2 & Efficiency
(cd / A) Lifetime
T (90) CIE x y Comparative Example (9) Comparative compound 1 5.9 5.1 300.0 5.9 85.5 0.32 0.61 Comparative Example (10) Comparative compound 2 5.7 4.3 300.0 6.1 95.5 0.32 0.62 Comparative Example (11) Comparative compound 3 6.1 5.2 300.0 5.8 80.8 0.32 0.62 Comparative Example (12) Comparative Compound 4 6.2 5.3 300.0 5.6 78.3 0.32 0.61 Comparative Example (13) Comparative Compound 5 6.0 5.5 300.0 5.5 81.0 0.32 0.61 Comparative Example (14) Comparative Compound 6 6.1 4.3 300.0 5.7 76.7 0.32 0.62 Example (1) Compound (P-1) 5.5 4.3 300.0 7.0 125.9 0.32 0.61 Example (2) Compound (P-2) 5.5 4.3 300.0 6.9 135.1 0.32 0.62 Example (3) Compound (P-4) 5.5 4.2 300.0 7.2 129.2 0.32 0.61 Example (4) Compound (P-5) 4.9 3.2 300.0 9.4 159.3 0.32 0.61 Example (5) Compound (P-6) 4.9 3.1 300.0 9.8 158.3 0.32 0.62 Example (6) Compound (P-36) 5.6 4.7 300.0 6.3 105.3 0.32 0.61 Example (7) Compound (P-37) 5.6 4.6 300.0 6.6 102.1 0.32 0.61 Example (8) Compound (P-59) 5.5 4.1 300.0 7.2 139.9 0.32 0.61

As can be seen from the results of Table 6, the organic light emitting device using the compound according to the present invention having an indole core as a green phosphorescent emission auxiliary layer material has a lower driving voltage and higher luminous efficiency than Comparative Examples 9 to 14. And significant life improvement.

In particular, the compounds P-5 and P-6 of the present invention, which are indole cores substituted with phenyl groups at position 5, which showed superior characteristics as hole transport layer materials, have low driving voltage and high efficiency even when used as green phosphorescent auxiliary layer materials. And high lifespan gave the best results.

As described above, when the compound according to the present invention is applied to an organic electroluminescent device, the device exhibits excellent device characteristics. ), Organic transistors (organic TFTs), monochromatic or white lighting elements, and the like. In addition, the compound according to the present invention, in addition to the hole transport layer or the light emitting auxiliary layer, The same effect may be obtained even when used in a hole injection layer, a light emitting layer, a buffer layer, an electron injection layer, an electron transport layer, and the like.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (11)

Compound for an organic electroluminescent device, characterized in that one of the following formula (2) to formula (5).

In the above formulas (2) to (5),
Ⅰ) R _4, R ₅ is hydrogen, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₆ alkenyl group and a C ₆ ~ C ₂₀ aryl unsubstituted or substituted with a substituent selected from the group consisting of a C ₆ ~ C of the An aryl group of ₂₅ ; Or a C ₂ to C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of hydrogen, a C ₁ to C ₄ alkyl group, a C ₂ to C ₆ alkenyl group, a C ₆ to C ₂₀ aryl group, or
Or, ii) R ₄ and R ₅ are each a substituted or unsubstituted saturated or unsaturated ring bonded to each other,
a and b are the integers of 1-5, respectively. delete The method of claim 1,
Formula (2) to Formula (5) is a compound for an organic electroluminescent device, characterized in that used as a light emitting auxiliary layer of the organic light emitting device. The method of claim 1,
Compound for an organic electroluminescent device, characterized in that one of the following compounds.

In an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer positioned between the first electrode and the second electrode,
The organic material layer is an organic electroluminescent device comprising the compound of any one of claims 1, 3 and 4. 6. The method of claim 5,
An organic electric device, characterized in that to form the compound to the organic material layer by a solution process. 6. The method of claim 5,
The organic material layer comprises at least one of a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a hole injection layer, an electron injection layer and an electron transport layer. delete 6. The method of claim 5,
The organic material layer includes a light emitting auxiliary layer and a light emitting layer, wherein the compound is an organic electric device, characterized in that contained in the light emitting auxiliary layer. A display device comprising the organic electroluminescent device of claim 5; And
A controller for driving the display device; &Lt; / RTI &gt; The method of claim 10,
The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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