WO2020159099A1 - Organic electroluminescent composition and organic electroluminescent element comprising same - Google Patents

Abstract

The present invention relates to a compound derivative used in an organic electroluminescent element, and an organic electroluminescent element using the same, and more specifically, to an indolocarbazole derivative compound having an amine substituent. When the indolocarbazole derivative compound is used as a light emitting material in the organic layer of the organic electroluminescent element, the effect can be achieved in which high light emitting efficiency can be obtained even with a low driving voltage.

Description

Organic electroluminescent composition and organic electroluminescent device comprising same

The present invention relates to an organic electroluminescent device, and more particularly, to an indolocarbazole derivative compound used as a light emitting material for an organic electroluminescent device, and more specifically, an indolocarbazole derivative compound having an amine substituent, an organic compound containing the same It relates to an electroluminescent composition, and an organic electroluminescent device comprising the same.

Organic electroluminescent devices, which have several advantages such as low voltage driving, self-emission, light weight, thin viewing angle, and fast response speed, are one of the next-generation flat panel displays and have been actively researched in recent years.

The organic electroluminescent device is generally composed of an organic thin film structure between an anode and a cathode. The organic layer adjacent to the anode contains a hole transport material and has a function of mainly transmitting only holes in the organic electroluminescent device. Similarly, the organic layer adjacent to the cathode contains an electron transport material and has a function of mainly transmitting only electrons in the organic electroluminescent device. Holes and electrons injected from the anode and the cathode recombine in the light emitting layer, and then return from the excited state to the ground state to emit light.

The organic film of the organic electroluminescent device is not a simple structure, but by using a multi-layer structure including a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer or an electron injection layer composed of a host and a dopant It was possible to improve the performance of the organic electroluminescent device.

In order to improve light emission characteristics such as driving voltage and luminous efficiency of the organic electroluminescent device and to extend the life of the device for a long time, it is necessary to continuously research and develop organic thin film materials used in the organic electroluminescent device.

In this regard, the present inventors have registered with the Republic of Korea Patent No. 10-1555816 (announcement date: 2015.09.25., the name of the invention: an organic electroluminescent composition and an organic electroluminescent device comprising the same), Republic of Korea Registered Patent No. 10-1529878 ( Publication date: 2015.06.18., Name of invention: Organic electroluminescent composition and organic electroluminescent device comprising the same, Republic of Korea Patent No. 10-1627211 (Publication date: 2016.06.13., Title of invention: Aromatic compound containing Through the organic electroluminescent composition and the organic electroluminescent device comprising the same), various aromatic amine derivative compounds were invented. The compounds described herein have high luminescence brightness and luminous efficiency.

However, there is a need for a new compound that operates at a lower driving voltage than the existing one and has a higher luminous efficiency.

The present invention for solving the above problems is to provide a compound having a high luminous efficiency even with a low driving voltage when used as a light emitting material in the organic layer of the organic electroluminescent device.

In addition, the present invention has an object to provide a compound having excellent thermal stability, an organic electroluminescent composition comprising the same, and an organic electroluminescent device.

In addition, another object of the present invention is to provide a novel compound and a method for manufacturing the same, which can improve the luminous efficiency of the organic electroluminescent device and increase the life of the device.

In addition, another object of the present invention is to provide an organic electroluminescent device having high luminous efficiency and extended life.

The present invention is a compound represented by the following formula (I).

[Formula I]

In the above formula (I), L ₁ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenyl It's Rengi,

L ₂ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a linker )ego,

R ₁ is one of the structures represented by Formula II below,

[Formula II]

(In the formula II, R ₁₁ and R ₁₂ are hydrogen atom, deuterium atom, halogen group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted silyl group, or a cyano group,

X is an oxygen atom, a sulfur atom, CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group),

d and e are integers from 0 to 4, and when 2 or more, the substituents in parentheses are the same or different, and)

R ₂ to R ₅ are each independently of each other a hydrogen atom, a deuterium atom, a halogen group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy Is a group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, or a cyano group,

a is an integer from 0 to 3, b and c are integers from 0 to 4, and when a to c are 2 or more, the substituents in parentheses are the same or different.

Specific details of other embodiments are included in the detailed description and drawings.

When the compound according to the present invention is used as a light emitting material in the organic layer of the organic electroluminescent device, there is an effect that the light emission efficiency is high even with a low driving voltage.

In addition, the compound according to the present invention has a high glass transition temperature and thermal decomposition temperature, and thus has excellent thermal stability, and the composition containing the same is used in an organic electroluminescent device to evaluate the luminescence properties. As a result, the current density, brightness, maximum It showed excellent luminescence properties in several aspects of luminance and luminous efficiency.

In addition, when the organic electroluminescent device is manufactured using the compound according to the present invention, it is possible to simultaneously solve the problems of low luminescence brightness and low luminous efficiency, which are the biggest disadvantages of the existing organic electroluminescent device, as well as high glass transition temperature. Therefore, since the thermal stability of the organic electroluminescent device is excellent, it is possible to manufacture a high-performance organic electroluminescent device, and can greatly contribute to commercialization of an organic electroluminescent device requiring high efficiency, high brightness and long life.

1 is a view showing a multilayer structure of an organic electroluminescent device manufactured using an aromatic amine derivative according to an embodiment of the present invention.

Figure 2 is UV / Vis. of the compound 2 according to an embodiment of the present invention. Absorbance, fluorescence PL and low temperature PL spectrum graphs.

3 is a differential scanning calorimeter (DSC) curve graph of Compound 2 according to an embodiment of the present invention.

The present invention can be applied to a variety of transformations and may have various embodiments, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In the description of the present invention, when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted.

The terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.

The present invention is a compound represented by the following formula (I). Specifically, the present invention is an aromatic amine derivative useful for use as an organic electroluminescent material in an organic electroluminescent device, and is an indolocarbazole derivative compound having an amine substituent. Since the compound according to the present invention has a high glass transition temperature, excellent hole injection, and transport ability, when an organic electroluminescent device is manufactured using the compound, the luminous efficiency can be further improved even at a low driving voltage, thereby increasing the life of the device. Can be increased.

[Formula I]

In the above formula (I), L ₁ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenyl It's Rengi,

L ₂ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a linker )ego,

R ₁ is one of the structures represented by Formula II below,

[Formula II]

(In the formula II, R ₁₁ and R ₁₂ are hydrogen atom, deuterium atom, halogen group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted silyl group, or a cyano group,

X is an oxygen atom, a sulfur atom, CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group),

d and e are integers from 0 to 4, and when 2 or more, the substituents in parentheses are the same or different, and)

R ₂ to R ₅ are each independently of each other a hydrogen atom, a deuterium atom, a halogen group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy Is a group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, or a cyano group,

a is an integer from 0 to 3, b and c are integers from 0 to 4, and when a to c are 2 or more, the substituents in parentheses are the same or different.

In the above formula (I), substituted or unsubstituted means substituted by any functional group known in the art or not substituted by any functional group, wherein the functional group is a group of organic groups having common chemical properties. It refers to a common atomic group that contributes to its properties in a compound, or a bond form thereof.

In Formula I, L ₁ or/and L ₂ may be a substituted or unsubstituted arylene group, heteroarylene group, heterocyclic group, alkylene group, or alkenylene group. That is, the present invention is characterized in that the indolocarbazole and the amine substituent include a heterocyclic aromatic group such as a fluorene group in a central structure formed by an aromatic ring.

The arylene group may be arenediyl groups in which hydrogen atoms are removed one by one from carbon atoms at both ends of the arenes, and the alkylene group is at both ends of the alkane. It is possible to form hydrogen atoms one by one (-CnH2n-) from the carbon atom (for example, propylene), and the alkenylene group may be one in which the hydrogen atom is removed from the carbon atom at both ends of the alkene. Can.

The present inventors have researched for a long period of time on various aromatic amine derivative compounds exhibiting excellent luminescence properties, and as a result, the central structure of the compound is made by connecting indolocarbazole and an amine substituent by an aromatic ring. After confirming that the compound containing a functional group having a heterocyclic aromatic group, such as an orene group, exhibits better luminescence properties than the prior art, the present invention was completed.

As can be seen in the examples to be described later, when the compound according to the present invention is used as a light emitting material in an organic layer of an organic electroluminescent device, it is possible to have a high luminous efficiency even at a lower driving voltage than other conventional compounds.

The compound according to the present invention is structurally different from other compounds in the related art, and has excellent thermal stability because it has a high glass transition temperature and a thermal decomposition temperature.

So, the compound according to the present invention may be used as a light emitting material for an organic light emitting diode (Organic Light Emitting Diode). When an organic electroluminescent device is manufactured using the compound according to the present invention, it is possible to simultaneously solve the problems of low emission luminance and low luminous efficiency, which are the biggest disadvantages of the existing organic electroluminescent device, as well as high glass transition temperature. Since the thermal stability of the electroluminescent device is excellent, it is possible to manufacture a high-performance organic electroluminescent device, and can greatly contribute to commercialization of an organic electroluminescent device requiring high efficiency, high brightness and long life.

As an embodiment of the present invention, the formula (I) may be a compound characterized by the following formula (III) or formula (IV).

[Formula III] [Formula IV]

In Formulas III and IV, L ₂ , R ₁ to R ₅ , and a to c are as defined in Formula I, and L ₃ is a substituted or unsubstituted arylene group or a substituted or unsubstituted heterocyclic group. .

That is, L ₁ in Formula I or L ₃ in Formula III is more preferably an arylene group or a heterocyclic group. In other words, the present invention is characterized in that the indolocarbazole and the amine substituent include a heterocyclic aromatic group such as a fluorene group in a central structure formed by an aromatic ring, and the aromatic ring is an arylene group or heteroaryl. It may be an alkylene group, a heterocyclic group, an alkylene group, or an alkenylene group, and more preferably an arylene group or a heterocyclic group.

As can be seen in the examples to be described later, when L ₁ of Formula (I) or L ₃ of Formula (III) is an arylene group or a heterocyclic group, it exhibits more excellent luminescence properties than before.

In addition, as an embodiment of the present invention, the formula I may be a compound characterized in that the following formula V, formula VI, or formula VII.

[Formula V] [Formula VI] [Formula VII]

In Formula V, Formula VI, and Formula VII, L ₁ , R ₂ to R ₅ , R ₁₁ , and a to c are as defined in Formula I, and d is as defined in Formula II, and R ₆ and R ₇ are each independently of each other a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.

Along with this, it is more preferable that L ₂ in Formula I is a linker as an embodiment of the present invention.

That is, in Formula (I), R ₁ may have a basic structure of a fluorene group such as Formula (II), X in Formula (II) may be an oxygen atom, a sulfur atom, or CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group). , Especially, X is more preferably CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group).

[Formula II]

In other words, the formula (II) may be based on a dibenzofuran group in which X is an oxygen atom, or may be based on a dibenzothiophene group in which X is a sulfur atom, and X is CY ₂ (Y is a hydrogen atom, an alkyl group, or It may also be a fluorene group). Among them, X is more preferably CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group).

As can be seen in the Examples described later, in the formula (I) R ₁ has the structure of formula (II) (R ₁ is a dibenzofuran group, dibenzothiophene group, or fluorene group, that is, the above When Formula (I) is Formula (V), Formula (VI, or Formula (VII)), it exhibits better light emission characteristics than before. Among them, when R ₁ is a fluorene group (Formula I is Formula VII), the hole mobility is excellent, and thus, in all cases used as a hole transport layer or an electron blocking layer, it exhibits more excellent luminescence properties.

In addition, as an embodiment of the present invention, the formula (I) may be a compound characterized by the following formula (VIII) or formula (IX).

[Formula VIII] [Formula IX]

In Formula VIII, and Formula IX, L ₂ , R ₁ , R ₃ to R ₅ , and a to c are as defined in Formula I, and L ₃ is a substituted or unsubstituted arylene group or a substituted or unsubstituted It is a heterocyclic group.

That is, in Formula (I), R ₂ is more preferably an aryl group. In other words, in the present invention, the amine substituent has two functional groups (or functional groups), at least one (R ₁ ) has the structure of Formula II as described above, and the other (R ₂ ) is a hydrogen atom, a deuterium atom. , A halogen group, an aryl group, a heteroaryl group, an alkyl group, an aryloxy group, an alkoxy group, an alkoxycarbonyl group, an amino group, a silyl group, or a cyano group, among which the other (R ₂ ) is more preferably an aryl group desirable.

As can be seen from the examples described below, when R ₂ in the formula (I) is an aryl group (or biphenyl), when the compound is used in the hole transport layer or the electron blocking layer, the luminous efficiency and lifetime of the device It was further improved.

According to the above, the formula (I) of the present invention may be characterized by being selected from the group consisting of the following compounds. The present invention is an aromatic amine derivative having the structure of Formula I, and a specific example enabling an organic electroluminescent device having a particularly high luminous efficiency and a long life includes at least one selected from the following structural formula. However, the present invention is not limited to these.

The present invention may be an indolocarbazole derivative that can be used as a light emitting material for an organic electroluminescent device or an organic light emitting composition or an organic light emitting material including the same. That is, the present invention may be an organic electroluminescent composition comprising the compound described above and used as a light emitting material for an organic light emitting diode. In addition, the present invention may also be an organic electroluminescent composition comprising the above-mentioned compound and being used for a hole transport layer or an electron blocking layer of an organic light emitting diode.

When a derivative, composition, or material according to the present invention is used in an organic electroluminescent device, excellent luminous efficiency can be obtained, and a device having excellent durability can be manufactured because the glass transition temperature of the indolocarbazole derivative is high. Here, the indolocarbazole derivative compound is a material that can be used as a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, or a light emitting layer or a dopant, and preferably, used as a hole transport layer or an electron blocking layer When the most effective.

The organic light emitting composition and the organic electroluminescent device comprising the same according to the present invention include organic light emitting diodes, organic field-effect transistors, organic thin film transistors, organic laser diodes, organic solar cells, organic light emitting electrochemical cells, and organic integrated circuits Can also be used in the field.

In addition, the aromatic amine derivatives according to the present invention can be purified by recrystallization and sublimation due to the characteristics of the organic electroluminescent device requiring high purity.

In addition, another embodiment of the present invention is an organic electroluminescent device comprising at least one organic layer made of the above-described organic electroluminescent composition. Here, the organic electroluminescent device includes an organic light emitting diode, an organic field-effect transistor, an organic thin film transistor, an organic laser diode, an organic solar cell, an organic light emitting electrochemical cell or an organic integrated circuit, and the present invention provides the above organic light emitting. It is apparent to those skilled in the art that it can be applied in various ways, such as diodes.

Hereinafter, the present invention may be better understood by the following examples, and the following examples are for illustrative purposes of the present invention, and are not intended to limit the protection scope defined by the appended claims. .

[Example 1] Preparation of compound 1

1-1. Preparation of compound 1-1

To a 500-mL, 3-neck round bottom flask, 9.7 g (0.058 mol) of compound carbazole was added under a nitrogen atmosphere and diluted with 200 mL of dimethyl sulfoxide. To this diluent, 15-g of 1,2-dibromobenzene, 3.7 g of copper powder, and 12 g of potassium carbonate were added and stirred for 30 minutes at room temperature. The reaction solution was heated to reflux for 20 hours. The reaction solution was cooled to room temperature, and extracted with dichloromethane and distilled water. After drying the extract, it was concentrated under reduced pressure to obtain 10.3 g of compound 1-1 (yield 55%).

1-2. Preparation of compound 1-2

3000-mL, 4-neck round bottom flask Compound 1-1 prepared in Example 1-1 22 g (0.069 mol) of palladium acetate (II) 1.6 g, triphenylphosphine 3.6 g, potassium carbonate 43 g tetrabutyl 11 g of ammonium bromide and 2200 mL of dimethylacetamide were added. The reaction solution was stirred at 150° C. for 20 hours, and then dimethylacetamide was concentrated under reduced pressure. The concentrated solution was diluted with dichloromethane and extracted with dichloromethane and distilled water. After drying the extract, the crude product obtained by concentration under reduced pressure was separated by column to obtain 7.8 g of compound 1-2 (yield 47%).

1-3. Preparation of compound 1-3

Into a 500-mL, 3-neck round bottom flask, 6.5 g (0.027 mol) of compound 1-2 prepared in Example 1-2 was added and diluted with 162 mL of chloroform. After cooling this dilution to 0°C, 4.8 g of N -bromosuccinimide (NBS) was slowly added and stirred at room temperature for 12 hours. After adding 160 mL of distilled water to the reaction solution, the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized with acetonitrile and ethyl acetate and dried in vacuo to obtain 5.4 g of compound 1-3 (yield 63%).

1-4. Preparation of compound 1-4

17.4 g (0.054 mol) of compound 1-3 prepared in Example 1-3 was added to a 1000-mL, 4-neck round bottom flask and diluted with 350 mL of tetrahydrofuran. (4-chlorophenyl) boronic acid 9.4 g, 3M-potassium carbonate aqueous solution 54 mL and tetrakis(triphenylphosphine)palladium(0) 1.0 g were added to the diluted solution, and the reaction solution was refluxed for 6 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was dried in vacuo to obtain 17.1 g of compound 1-4 (yield 89%).

1-5. Preparation of compound 1

250-mL, a compound 1-4 8.0 g (0.023 mol) prepared in Example 1-4, 3-neck round bottom flask was charged with N - phenyl-9,9-dimethyl -9 H - fluorene-2-amine 7.1 g , Palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL was added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 11.0 g of compound 1 (yield 80%).

[Example 2] Preparation of compound 2

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 3.4 g of compound 2 (yield 87%).

[Example 3] Preparation of compound 3

N -((1,1`-biphenyl)-3-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Was added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 10.3 g of compound 3 (yield 67%).

[Example 4] Preparation of compound 4

N -((1,1`-biphenyl)-2-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 12.8 g of compound 4 (83% yield).

[Example 5] Preparation of compound 5

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask - diphenyl -9 H-fluorene-2-amine 11.6 g ,, palladium acetate (II) 0.03 g, tree - (t- butyl) phosphine 0.05 g, sodium t- butoxide, and 2.8 g o-xylene 80 mL was added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 13.0 g of compound 5 (yield 71%).

[Example 6] Preparation of compound 6

N -((1,1`-biphenyl)-2-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask - diphenyl -9 H-fluorene-2-amine 11.6 g ,, palladium acetate (II) 0.03 g, tree - (t- butyl) phosphine 0.05 g, sodium t- butoxide, and 2.8 g o-xylene 80 mL was added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 12.8 g of compound 6 (yield 70%).

[Example 7] Preparation of compound 7

To 250-mL, 3-neck round bottom flask, 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4, 6.5 g of N -phenyldibenzo[b,d]-furan-4-amine, palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL were added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.7 g of compound 7 (yield 74%).

[Example 8] Preparation of compound 8

N -((1,1`-biphenyl)-4-yl)dibenzo[b] in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask. 8.4 g of ,d]-furan-4-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene were added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 10.4 g of compound 8 (yield 70%).

[Example 9] Preparation of compound 9

In a 250-mL, 3-neck round bottom flask, 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 was added with 8.4 g of N ,6-diphenyldibenzo[b,d]-furan-4-amine. , Palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL was added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.2 g of compound 9 (yield 62%).

[Example 10] Preparation of compound 10

To 250-mL, 3-neck round bottom flask, 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 was added with 6.5 g of N -phenyldibenzo[b,d]furan-3-amine, palladium acetate ( II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL were added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.0 g of compound 10 (yield 61%).

[Example 11] Preparation of compound 11

N -((1,1`-biphenyl)-2-yl)dibenzo[b] in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask. 8.4 g of ,d]furan-4-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene were added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.6 g of compound 11 (yield 65%).

[Example 12] Preparation of compound 12

12-1. Preparation of compound 12-1

17.4 g (0.054 mol) of compound 1-3 prepared in Example 1-3 was added to a 1000-mL, 4-neck round bottom flask and diluted with 350 mL of tetrahydrofuran. To this dilution, 9.4 g of (3-chlorophenyl) boronic acid, 54 mL of 3M-potassium carbonate aqueous solution and 1.0 g of tetrakis(triphenylphosphine)palladium (0) were added, and the reaction solution was refluxed for 6 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was dried in vacuo to obtain 15.5 g of compound 12-1 (yield 81%).

12-2. Preparation of compound 12

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 12-1 prepared in Example 12-1 in 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 13.1 g (yield 85%) of compound 12 .

[Example 13] Preparation of compound 13

N -((1,1`-biphenyl)-2-yl)-9,9 in 8.0 g (0.023 mol) of compound 12-1 prepared in Example 12-1 in 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 11.6 g of compound 13 (75% yield).

[Example 14] Preparation of compound 14

N -((1,1`-biphenyl)-4-yl)dibenzo[b] in 8.0 g (0.023 mol) of compound 12-1 prepared in Example 12-1 in a 250-mL, 3-neck round bottom flask. 8.4 g of ,d]-furan-4-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene were added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 8.6 g (58% yield) of compound 14 .

[Example 15] Preparation of compound 15

15-1. Preparation of compound 15-1

17.4 g (0.054 mol) of compound 1-3 prepared in Example 1-3 was added to a 1000-mL, 4-neck round bottom flask and diluted with 350 mL of tetrahydrofuran. To this dilution, 9.4 g of (2-chlorophenyl) boronic acid, 54 mL of 3M-potassium carbonate aqueous solution and 1.0 g of tetrakis(triphenylphosphine)palladium (0) were added, and the reaction solution was refluxed for 6 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was dried in vacuo to obtain 15.0 g of compound 15-1 (78% yield).

15-2. Preparation of compound 15

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 15-1 prepared in Example 15-1 in 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 10.8 g of compound 15 (yield 70%).

[Example 16] Preparation of compound 16

N -((1,1`-biphenyl)-2-yl)-9,9 in 8.0 g (0.023 mol) of compound 15-1 prepared in Example 15-1 in 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 4 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 12.3 g of compound 16 (yield 80%).

[Example 17] Preparation of compound 17

To 250-mL, 3-neck round bottom flask, 8.0 g (0.023 mol) of compound 15-1 prepared in Example 15-1, 6.5 g of N -phenyldibenzo[b,d]-furan-4-amine, palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL were added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 8.4 g of compound 17 (yield 64%).

[Example 18] Preparation of compound 18

In a 250-mL, 3-neck round bottom flask, 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 was added with 8.4 g of N ,6-diphenyldibenzo[b,d]thiophen-4-amine. , Palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL was added. The reaction solution was refluxed for 5 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and separated by a column to obtain 8.1 g of compound 18 (yield 53%).

[Example 19] Preparation of compound 19

250-mL, 3 gu a solution of the compound prepared in Example 1-4 to 1-4 round bottom flask 8.0 g bis (0.023 mol) (9,9- dimethyl -9 H - fruit fluoren-2-yl) amine 10.1 g , Palladium acetate (II) 0.03 g, tri-(t-butyl)phosphine 0.05 g, sodium t-butoxide 2.8 g and o -xylene 80 mL was added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.8 g of compound 19 (yield 60%).

[Example 20] Preparation of compound 20

20-1. Preparation of compound 20-1

And poured fluorene-2-amine 12.1 g (0.058 mol), diluted with toluene 360 mL - 500-mL, 3-dimethyl-9,9-gu -9 H in a nitrogen atmosphere in a round bottom flask. To this diluent, 20.3 g of 2-(4-bromophenyl)-9,9-dimethyl-9 H -fluorene, tris(dibenzylideneacetone)dipalladium(0) 0.27 g, tri-(t-butyl)phos 0.12 g of pin and 7.2 g of sodium t-butoxide were added. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 16.6 g of compound 20-1 (60% yield).

20-2. Preparation of compound 20

250-mL, 3-neck round bottom flask 1-4 g of compound 1-4 prepared in Example 1-4 (0.023 mol) 11.0 g of compound 20-1 prepared in Example 20-1, palladium acetate (II) 0.03 g, 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene were added. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 9.9 g of compound 20 (yield 55%).

[Example 21] Preparation of compound 21

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-1-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 4 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 10.5 g of compound 21 (68% yield).

[Example 22] Preparation of compound 22

N -((1,1`-biphenyl)-4-yl)-9,9 in 8.0 g (0.023 mol) of compound 1-4 prepared in Example 1-4 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-4-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 2 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 12.2 g of compound 22 (yield 79%).

[Example 23] Preparation of compound 23

23-1. Preparation of compound 23-1

1000-mL, 4 were added to obtain the compound embodiments 1 -3 17.4 g (0.054 mol) prepared in Example 1-3 in a round bottom flask and diluted with 350 mL of tetrahydrofuran. To this diluent, (4`-chloro-(1,1`-biphenyl)-4-yl) boronic acid 13.9 g, 3M-potassium carbonate aqueous solution 54 mL and tetrakis(triphenylphosphine) palladium (0) After adding 1.0 g, the reaction solution was refluxed for 6 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was dried in vacuo to obtain 17.3 g (yield 74%) of compound 23-1 .

23-2. Preparation of compound 23

N -((1,1`-biphenyl)-2-yl)-9,9 in 9.8 g (0.023 mol) of compound 23-1 prepared in Example 23-1 in a 250-mL, 3-neck round bottom flask 9.2 g of dimethyl-9 H -fluoren-2-amine, 0.03 g of palladium acetate (II), 0.05 g of tri-(t-butyl)phosphine, 2.8 g of sodium t-butoxide and 80 mL of o -xylene Input. The reaction solution was refluxed for 3 hours, then cooled and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried under vacuum, and then separated by a column to obtain 15.1 g of compound 23 (yield 88%).

[Example 24]

After completely washing the substrate formed with a transparent anode of indium tin oxide (ITO) having a thickness of 1200 mm 2, the substrate was put into a vacuum deposition apparatus and then depressurized to about 10 ⁻⁷ torr. Subsequently, the following compound RHI was deposited to have a thickness of 50 MPa to form a hole injection layer. Subsequently, the hole transport layer was formed by depositing the compound 1 of the present invention to have a thickness of 800 MPa. Subsequently, the following compound RHT2 was deposited to have a thickness of 150 MPa to form an electron blocking layer. Subsequently, the following compound BH1 which is a blue host and the following compound BD1 which is a blue dopant were simultaneously deposited in a weight ratio of 97:3 to form a light emitting layer so that the thickness was 250 MPa. Subsequently, an electron transport layer 1 was formed by depositing the compound EET1 of the ELM product so that the thickness was 200 MPa. Subsequently, the electron transport layer 2 was formed by depositing the compound EET2 of the ELM product so as to have a thickness of 50 MPa. Subsequently, an electron injection layer was formed by depositing lithium fluoride (LiF) to a thickness of 15 MPa. Finally, aluminum was deposited to a thickness of 2000 MPa to form a cathode. A light emission test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. Table 1 shows the applied voltage, luminous efficiency, and luminous color measured at a luminance of 500 cd/m ² .

[Example 25]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 2 was used instead of Compound 1 as the hole transport layer.

[Example 26]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 3 was used instead of Compound 1 as the hole transport layer.

[Example 27]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 4 was used instead of Compound 1 as the hole transport layer.

[Example 28]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 5 was used instead of Compound 1 as the hole transport layer.

[Example 29]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 6 was used instead of Compound 1 as the hole transport layer.

[Example 30]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 15 was used instead of Compound 1 as the hole transport layer.

[Example 31]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 16 was used instead of Compound 1 as the hole transport layer.

[Example 32]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 19 was used instead of Compound 1 as the hole transport layer.

[Example 33]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 21 was used instead of Compound 1 as the hole transport layer.

[Example 34]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 22 was used instead of Compound 1 as the hole transport layer.

[Example 35]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound 23 was used instead of Compound 1 as the hole transport layer.

[Example 36]

After completely washing the substrate formed with a transparent anode of indium tin oxide (ITO) having a thickness of 1200 mm 2, the substrate was put into a vacuum deposition apparatus and then depressurized to about 10 ⁻⁷ torr. Subsequently, the following compound RHI was deposited to have a thickness of 50 MPa to form a hole injection layer. Subsequently, the compound RHT1 was deposited to have a thickness of 800 MPa to form a hole transport layer. Subsequently, the compound 2 of the present invention was deposited to have a thickness of 150 MPa to form an electron blocking layer. Subsequently, the following compound BH1 which is a blue host and the following compound BD1 which is a blue dopant were simultaneously deposited in a weight ratio of 97:3 to form a light emitting layer so that the thickness was 250 MPa. Subsequently, an electron transport layer 1 was formed by depositing the compound EET1 of the ELM product so that the thickness was 200 MPa. Subsequently, the electron transport layer 2 was formed by depositing the compound EET2 of the ELM product so as to have a thickness of 50 MPa. Subsequently, an electron injection layer was formed by depositing lithium fluoride (LiF) to a thickness of 15 MPa. Finally, aluminum was deposited to a thickness of 2000 MPa to form a cathode. A light emission test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. Table 1 shows the applied voltage, luminous efficiency, and luminous color measured at a luminance of 500 cd/m ² .

[Example 37]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 4 was used instead of Compound 2 as the electron blocking layer.

[Example 38]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 5 was used instead of Compound 2 as the electron blocking layer.

[Example 39]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 6 was used instead of Compound 2 as the electron blocking layer.

[Example 40]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 7 was used instead of Compound 2 as the electron blocking layer.

[Example 41]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 8 was used instead of Compound 2 as the electron blocking layer.

[Example 42]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 9 was used instead of Compound 2 as the electron blocking layer.

[Example 43]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 10 was used instead of Compound 2 as the electron blocking layer.

[Example 44]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 11 was used instead of Compound 2 as the electron blocking layer.

[Example 45]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 12 was used instead of Compound 2 as the electron blocking layer.

[Example 46]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 13 was used instead of Compound 2 as the electron blocking layer.

[Example 47]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 14 was used instead of Compound 2 as the electron blocking layer.

[Example 48]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 15 was used instead of Compound 2 as the electron blocking layer.

[Example 49]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 16 was used instead of Compound 2 as the electron blocking layer.

[Example 50]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 17 was used instead of Compound 2 as the electron blocking layer.

[Example 51]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 18 was used instead of Compound 2 as the electron blocking layer.

[Example 52]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 20 was used instead of Compound 2 as the electron blocking layer.

[Example 53]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 21 was used instead of Compound 2 as the electron blocking layer.

[Example 54]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 22 was used instead of Compound 2 as the electron blocking layer.

[Example 55]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound 23 was used instead of Compound 2 as the electron blocking layer.

[Example 56]

In Example 42, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 42, except that Compound 2 was used instead of Compound RHT1 as the hole transport layer.

[Example 57]

In Example 45, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 45, except that Compound 2 was used instead of Compound RHT1 as the hole transport layer.

[Example 58]

In Example 46, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 46, except that Compound 2 was used instead of Compound RHT1 as the hole transport layer.

[Example 59]

In Example 46, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 46, except that Compound 4 was used instead of Compound RHT1 as the hole transport layer.

[Example 60]

In Example 54, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 54, except that Compound 21 was used instead of Compound RHT1 as the hole transport layer.

[Comparative Example 1]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that Compound RHT1 was used instead of Compound 1 as the hole transport layer.

[Comparative Example 2]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that the following compound EHT1 was used instead of Compound 1 as the hole transport layer.

[Comparative Example 3]

In Example 24, an organic electroluminescent device was fabricated and evaluated in the same manner as in Example 24, except that Compound EHT2 was used instead of Compound 1 as the hole transport layer.

[Comparative Example 4]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that the compound EHT3 below was used instead of Compound 1 as the hole transport layer.

[Comparative Example 5]

In Example 24, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 24, except that the compound EHT4 below was used instead of Compound 1 as the hole transport layer.

[Comparative Example 6]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound EHT5 was used instead of Compound 2 as the electron blocking layer.

[Comparative Example 7]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound EHT6 was used instead of Compound 2 as the electron blocking layer.

[Comparative Example 8]

In Example 36, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 36, except that Compound EHT7 was used instead of Compound 2 as the electron blocking layer.

Organic electroluminescent devices of Examples 24 to 60 and Comparative Examples 1 to 8 were manufactured using the compounds prepared according to Examples 1 to 23 as described above. The hole transport layer and electron blocking layer materials, driving voltage, luminous efficiency, and luminous color are summarized in Table 1 below.

Example	Hole transport layer material	Electronic blocking layer material	Driving voltage (V)	Luminous efficiency (cd/A)	Emission color
Example 24	Compound 1	RHT2	4.2	7.1	blue
Example 25	Compound 2	RHT2	3.9	7.8	blue
Example 26	Compound 3	RHT2	4.2	7.6	blue
Example 27	Compound 4	RHT2	3.8	7.9	blue
Example 28	Compound 5	RHT2	4.3	7.6	blue
Example 29	Compound 6	RHT2	4.2	7.1	blue
Example 30	Compound 15	RHT2	4.1	7.2	blue
Example 31	Compound 16	RHT2	4.2	7.4	blue
Example 32	Compound 19	RHT2	4.4	7.0	blue
Example 33	Compound 21	RHT2	4.0	7.6	blue
Example 34	Compound 22	RHT2	4.3	7.0	blue
Example 35	Compound 23	RHT2	4.5	7.1	blue
Example 36	RHT1	Compound 2	4.2	7.1	blue
Example 37	RHT1	Compound 4	4.1	7.3	blue
Example 38	RHT1	Compound 5	4.4	7.3	blue
Example 39	RHT1	Compound 6	4.3	7.5	blue
Example 40	RHT1	Compound 7	4.2	7.0	blue
Example 41	RHT1	Compound 8	4.5	7.3	blue
Example 42	RHT1	Compound 9	4.3	7.6	blue
Example 43	RHT1	Compound 10	4.5	7.0	blue
Example 44	RHT1	Compound 11	4.5	6.9	blue
Example 45	RHT1	Compound 12	4.1	7.8	blue
Example 46	RHT1	Compound 13	3.8	7.9	blue
Example 47	RHT1	Compound 14	4.4	6.8	blue
Example 48	RHT1	Compound 15	3.9	7.4	blue
Example 49	RHT1	Compound 16	4.1	7.6	blue
Example 50	RHT1	Compound 17	4.4	7.0	blue
Example 51	RHT1	Compound 18	4.5	6.9	blue
Example 52	RHT1	Compound 20	4.4	7.0	blue
Example 53	RHT1	Compound 21	4.3	7.1	blue
Example 54	RHT1	Compound 22	4.0	7.8	blue
Example 55	RHT1	Compound 23	4.5	6.9	blue
Example 56	Compound 2	Compound 9	4.0	7.7	blue
Example 57	Compound 2	Compound 12	3.8	7.9	blue
Example 58	Compound 2	Compound 13	3.8	8.0	blue
Example 59	Compound 4	Compound 13	3.6	8.2	blue
Example 60	Compound 21	Compound 22	3.7	7.9	blue
Comparative Example 1	RHT1	RHT2	5.6	5.5	blue
Comparative Example 2	EHT1	RHT2	4.9	6.6	blue
Comparative Example 3	EHT2	RHT2	5.2	6.2	blue
Comparative Example 4	EHT3	RHT2	5.3	6.0	blue
Comparative Example 5	EHT4	RHT2	4.7	6.6	blue
Comparative Example 6	RHT1	EHT5	5.1	6.3	blue
Comparative Example 7	RHT1	EHT6	5.3	6.0	blue
Comparative Example 8	RHT1	EHT7	5.3	5.7	blue

As can be seen from Table 1, the organic electroluminescent devices according to Examples 24 to 60 of the present invention can operate at a lower driving voltage than Comparative Examples 1 to 8, and have higher luminance and luminous efficiency. You can see that there is.

Specifically, all of the compounds 1 to 23 according to the above embodiment are the central structures in which both the indolocarbazole and the amine substituent are connected by an aromatic ring (more specifically, L ₁ in the formula (I) is an arylene group or a heterocyclic group). However, compared with the case (Comparative Examples 1 to 8), the driving voltage is lower and the luminous efficiency is higher.

In addition, in Formula II of the present invention, when X is CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group) (compounds 1-6, 12, 13, 15, 16, 19-23), X is an oxygen atom, And a lower driving voltage than the sulfur atom (compounds 7-11, 14, 17, 18).

In addition, in the general formula (I) of the present invention, when R ₂ is an aryl group (especially biphenyl) (compounds 2-6, 8, 11-16, 21-23), as a whole, than when not (compounds 19, 20) It showed better luminous efficiency at lower driving voltage.

In the above, the present invention has been illustrated and described in relation to a specific preferred embodiment, but the present invention may be variously modified and changed within the limits that do not depart from the technical features or fields of the present invention provided by the following claims. Being able is obvious to those of ordinary skill in the art.

Claims (10)

1. Compound represented by the formula (I):

   [Formula I]

   

   In the above formula (I), L ₁ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted alkenyl It's Rengi,

   L ₂ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a linker )ego,

   R ₁ is one of the structures represented by Formula II below,

   [Formula II]

   

   (In the formula II, R ₁₁ and R ₁₂ are hydrogen atom, deuterium atom, halogen group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted silyl group, or a cyano group,

   X is an oxygen atom, a sulfur atom, CY ₂ (Y is a hydrogen atom, an alkyl group, or an aryl group),

   d and e are integers from 0 to 4, and when 2 or more, the substituents in parentheses are the same or different, and)

   R ₂ to R ₅ are each independently of each other a hydrogen atom, a deuterium atom, a halogen group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy Is a group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, or a cyano group,

   a is an integer from 0 to 3, b and c are integers from 0 to 4, and when a to c are 2 or more, the substituents in parentheses are the same or different.
2. According to claim 1,

   A compound characterized by being used as a light emitting material for an organic light emitting diode (Organic Light Emitting Diode).
3. According to claim 1,

   The compound of the formula I is characterized by the following formula III or formula IV:

   [Formula III] [Formula IV]

   

   In Formula III and Formula IV, L ₂ , R ₁ to R ₅ , and a to c are as defined in Formula I,

   L ₃ is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heterocyclic group.
4. According to claim 1,

   Formula I is a compound characterized in that the following formula V, formula VI, or formula VII:

   [Formula V] [Formula VI] [Formula VII]

   

   In Formula V, Formula VI, and Formula VII, L ₁ , R ₂ to R ₅ , R ₁₁ , and a to c are as defined in Formula I, and d is as defined in Formula II,

   R ₆ and R ₇ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
5. According to claim 1,

   Formula I is a compound characterized in that the following formula VIII, or formula IX:

   [Formula VIII] [Formula IX]

   

   In Formula VIII, and Formula IX, L ₂ , R ₁ , R ₃ to R ₅ , and a to c are as defined in Formula I,

   L ₃ is a substituted or unsubstituted arylene group or a substituted or unsubstituted heterocyclic group.
6. According to claim 1,

   L ₂ is a linker.
7. According to claim 1,

   Formula I is a compound characterized in that selected from the group consisting of the following compounds:

   

   
8. It comprises a compound according to any one of claims 1 to 7,

   An organic electroluminescent composition, characterized in that it is used as a light emitting material for an organic electroluminescent device (Organic Light Emitting Diode).
9. It comprises a compound according to any one of claims 1 to 7,

   An organic electroluminescent composition characterized in that it is used in a hole transport layer or an electron blocking layer of an organic electroluminescent device (Organic Light Emitting Diode).
10. An organic electroluminescent device comprising at least one organic layer comprising the composition according to claim 8.

Images