KR20160054374A - Display device using a composition for organic electronic element, and an organic electronic element thereof - Google Patents

Abstract

The present invention provides an organic electronic element, a display device, and an electronic device comprising the same. The organic electronic element has improved light-emitting efficiency, stability and lifespan properties by using a composition consisting of two or more compounds which have different structures as a hole transport layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a display device and an organic electroluminescent device using a composition for an organic electroluminescent device,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device, a display device, and an electronic device using the composition of organic electroluminescent compound. More particularly, the present invention relates to a display device including an organic electroluminescent layer And an organic electric device.

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 electroluminescence device using an organic light emitting phenomenon is a self-luminous device using a principle that a light emitting material emits light by a recombination energy of holes injected from an anode and electrons injected from a cathode by applying a current.

The organic electroluminescent device may have a structure in which an anode is formed on a substrate, and a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are sequentially formed on the anode. Here, the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer are organic thin films made of organic compounds.

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption is an important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues as well as drive voltage issues are critical issues to be solved.

Particularly, in the case of driving voltage problem and lifetime problem, there are many problems associated with the thermal deterioration problem of the hole injecting material and the hole transporting material. For example, a method of forming a multilayer structure of a hole transporting layer (US Patent No. 5256945) and a method of using a material having a high glass transition temperature (U.S. Patent No. 5061569) have been proposed.

In addition, when a material having a good hole transport function is used to reduce the driving voltage, although the driving voltage of the device is greatly reduced, the efficiency and lifetime of the device are degraded due to excessive charge injection. There was an attempt.

However, there is a problem that the power consumption of the organic electronic device is increased and the lifetime is lowered due to the increase of the driving voltage of the progressive driving voltage of the blue organic electronic device such as red, green, and blue. In order to solve this problem, a buffer layer is formed between the anode and the hole transporting layer (Korean Patent Publication No. 2006-0032099).

In the present invention, two or more hole transporting materials having different band gaps are mixed in the hole transporting layer to reduce the thermal deterioration occurring at the interface between the hole transporting layer and the hole transporting layer and at the interface between the hole transporting layer and the light emitting layer, And an object of the present invention is to provide an organic electroluminescent device having an excellent luminous efficiency by efficiently controlling the amount of injected charges and increasing the efficiency.

The present invention provides a light emitting device comprising: a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a light emitting layer including at least one hole transport layer and a light emitting compound, wherein the hole transport layer has a different chemical structure And a display device including the organic electroluminescent device.

The present invention also relates to an organic electroluminescent device and a electronic device using the composition of the present invention, wherein the organic electroluminescent compound is different from each other among the compounds represented by the following general formula (1). More specifically, The present invention provides an organic electronic device using the composition in which two or more hole transporting materials having different chemical structures are mixed, and an electronic device including the same.

The organic electroluminescent device and the display device including the organic electroluminescent device provided in the present invention have the advantages that the thermal deterioration occurring at the interface between the hole injection layer and the hole transporting layer and the interface between the hole transporting layer and the light emitting layer is reduced and the lifetime is prolonged, Is efficiently controlled to provide excellent luminous efficiency.

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

Hereinafter, embodiments of the present invention will be described in detail. 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."

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group "," alkenyl group ", or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups , 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 "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl 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 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise specified, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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 specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

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

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group having 1 to 20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

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 ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

The organic electroluminescent device according to the present invention may be one of an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and 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. At this time, the electronic device may be a current or a 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, a display device and an organic electroluminescent device according to aspects of the present invention will be described.

The present invention relates to a plasma display panel comprising a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer comprises two kinds of carbazole compounds having different structures from each other, Wherein the composition ratio of each of the different structural formulas is selected from 5: 5 to 9: 1.

According to a specific example of the present invention, A second electrode; And an organic material layer disposed between the first electrode and the second electrode and including at least one hole transporting layer and a light emitting layer, wherein the hole transporting layer comprises a compound represented by the following general formula The present invention provides an organic electronic device characterized by comprising a composition in which two kinds of compounds are mixed.

{In the formula ¹ Ar 1 ~ Ar ³ are each independently selected from the group consisting of a heteroaryl group, fluorene-carbonyl of C _{6 ~ 60} aryl group, C _{2 ~ 60} of the, L ¹ is a single bond, C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60} heterocyclic group, fluorenyl group, and a divalent aromatic ring of C _{3 ~ 60} alicyclic and C _{6 ~ 60} of selected from the group consisting of a fused ring, m is And n is an integer of 0 ^{to 3} ; R ^{1 to} R ² are the same or different from each other and are independently selected from the group consisting of deuterium; Tritium; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; R ¹ and R ² are each a group selected from the group consisting of A plurality of R ^{1 s} or a plurality of R ^{2 s} may be bonded to each other to form a ring.

A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -L _{'-N (R a) (R} b); C 1 ~ Import alkylthio of C _20; C ₁ ~ alkoxy group of C _20; C ₁ ~ alkyl group of C _20; C ₂ ~ C ₂₀ alkenyl group a; ₂ C ~ alkynyl of C _20; an aryl group of C ₆ - C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; C ₂ - heterocyclic group of C _20; C of ₃ ~ C ₂₀ cycloalkyl An alkyl group, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term " ring " means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)}

More specifically, the compound represented by Formula 1 may include a compound represented by Formula 1-1 or 1-2, wherein the hole transport layer may contain a compound represented by Formula 1-1 or 1-2 below The organic electroluminescent device of the present invention includes a composition including two kinds of compounds having different structures.

(In the formulas 1-1 to 1-2, Ar ^1-3 , L ¹ , R ¹ , R ² , m and n are the same as defined above.)

In another specific example of the present invention, the organic electroluminescent device is characterized in that the compound represented by Formula 1 is represented by the following Formulas 1-3, 1-4, 1-5, or 1-6.

(Wherein Ar ¹ , Ar ² , R ¹ , R ² , L ¹ , m and n are as defined above, V and W are each independently S, O or CR R ', R "are each independently an aryl group of C _6-24 , a C _1-20 alkyl group, a C _2-20 alkenyl or C _1-20 alkoxy group, and R', R" And R ³ to R ⁶ are each independently selected from the group consisting of deuterium, tritium, cyano group, nitro group, halogen group, aryl group, alkenyl group, alkylene group, alkoxy group and heterocyclic group is selected from the group, R ³ together, R ⁴ to each other, bonded to each other to each other among R ^5, R ⁶ can be formed by the ring, and, a, o is an integer of 0-3, b, p is an integer from 0 to 4 to be.)

According to a specific example of the present invention, the compound of Chemical Formula 1 is one of the compounds represented by the following chemical formula, and provides an organic electronic device containing such a compound.

In another embodiment of the present invention, the two compounds represented by Formula 1 are represented by Formula 1, wherein Ar ¹ , Ar ² , and Ar ³ are both C _6-24 aryl groups. to provide.

In another aspect of the present invention, Ar ¹ , Ar ² , and Ar ³ of one of the two compounds represented by Formula 1 are all C _{6 to} C ₂₄ aryl groups; And at least one of Ar ¹ , Ar ² and Ar ³ of the remaining one kind of compound is dibenzothiophene or dibenzofuran.

In another specific embodiment, the present invention provides an organic electronic device comprising a composition comprising at least one of Ar ¹ , Ar ² , and Ar ³ of a compound represented by Formula 1, wherein each of Ar ¹ , Ar ² , and Ar ³ is dibenzothiophene or dibenzofuran.

In another specific example of the present invention, there is provided an organic electroluminescent device comprising a composition having a weight ratio of 10% to 90% when one of two compounds having different structures represented by the formula 1 is mixed have.

Specifically, in another aspect of the present invention, when two kinds of compounds having different structures represented by the formula 1 are mixed, the mixing ratio is 5: 5 or 6: 4 or 7: 3 or 8: 2 or 9: At least And a display device including the same.

As another example of the present invention, there is provided an organic electroluminescent device comprising at least one compound represented by the general formula (1) in a composition in which the compounds represented by the general formula (1) are mixed with each other, and a display Device.

The organic electroluminescent device of the present invention is characterized in that a compound represented by the general formula (1) is used as a luminescent auxiliary layer between a hole transport layer and a luminescent layer, which comprises a composition comprising two kinds of compounds having different structures represented by the general formula And a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.

The present invention provides an electronic device including a display device including the organic electronic devices of various examples described above and a control unit for driving the display device. The organic electroluminescent device may be an organic electroluminescent device, an organic photovoltaic cell, an organophotoreceptor, an organic transistor, or an element for monochromatic or white illumination.

Hereinafter, the synthesis examples of the compound represented by the formula (1) and the production example of the organic electroluminescent device of the present invention included in the organic electroluminescent device of the present invention will be specifically described. It is not.

[Synthesis Example]

The final product of Formula 1 according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Reaction Scheme 1>

Synthesis example of Sub 1 (L ^One Is not a single bond)

1) M1-2-1 Synthesis Example

After dissolving 3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) in 980 mL of DMF, bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol) 41.3 g, 420 mmol) were added in this order, and the mixture was stirred for 24 hours to synthesize a borate compound. 35.2 g (68%) of the obtained compound was separated by silicagel column and recrystallization.

2) M1-2-2 Synthesis Example

40 g (64%) was obtained through the same experimental method as M1-2-1.

3) Sub 1-1-1 Synthetic Example

M1-2-1 (29.5 g, 80 mmol) was dissolved in THF 360 mL, 4-bromo- 4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3) 4 ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and water (180 mL), and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 26.56 g (70%) of the product

4) Sub 1-1-2 Synthetic Example

M1-2-1 (29.5 g, 80 mmol) , THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh 3) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and water (180 mL), and the mixture was refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 22.9 g (72%) of the product

5) Sub 1-1-3 Synthetic Example

M1-2-1 (29.5 g, 80 mmol) was dissolved in THF 360 mL, 4'-bromo- 3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3) 4 ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and water (180 mL), and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 24.7 g (65%) of the product

6) Sub 1-1-4 Synthetic Example

After dissolving M1.2-2 (35.63 g, 80 mmol) obtained in the above synthesis in 360 mL of THF, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and water (180 mL), and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 29.51 g (67%) of the product

7) M1-2-3 Synthesis Example

After dissolving 2-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) in 980 mL of DMF, bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol) 41.3 g, 420 mmol) were added in this order, followed by stirring for 24 hours to synthesize a borate compound. Then, 36.2 g (70%) of the obtained compound was separated by silicagel column and recrystallization to obtain a candidate compound.

8) M1-2-4 Synthesis Example

43.6 g (67%) was obtained through the same experimental procedure as M1-2-3.

9) Sub 1-1-5 Synthetic Example

M1-2-3 (29.5 g, 80 mmol) was dissolved in THF 360 mL, 4-bromo- 4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3) 4 ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and water (180 mL), and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 26.95 g (70%) of the product

10) Sub 1-1-6 Synthesis Example

M1-2-3 (29.5 g, 80 mmol) , THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh 3) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water, 23.26 g (73%) of the product was obtained through the same experimental procedure as Sub 1-1-5

11) Sub 1-1-7 Synthetic Example

M1-2-3 (29.5 g, 80 mmol) was dissolved in THF 360 mL, 4'-bromo- 3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3) 4 ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were added, and 25.8 g (68%) of the product was obtained through the same experimental procedure as Sub 1-1-5

12) Sub 1-1-8 Synthesis Example

(35.63 g, 80 mmol) obtained in the above synthesis was dissolved in 360 mL of THF, and 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and water (180 mL), and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 30.4 g (69%) of the product.

 Synthetic example of Sub 2

Sub 2 of Scheme 1 can be synthesized by the reaction path of Scheme 2 below.

<Reaction Scheme 2>

Synthetic Example of Sub 2-28

4-bromo-1,1'-biphenyl ( 5.6g, 24mmol) was dissolved in toluene, [1,1'-biphenyl] -4- amine (3.4g, 20mmol), Pd 2 (dba) 3 (0.5 g , 0.6 mmol), P (t -Bu) 3 (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), toluene (300 mL) then was added to each, refluxed at 100 ℃ stirred for 24 hours . After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resultant organic material was purified by silicagel column and recrystallized to obtain 6.2 g (yield: 80%) of final compound.

Examples of Sub 2 include, but are not limited to, the following.

compound FD-MS compound FD-MS Sub 2-1 m / z = 169.09 (C ₁₂ H ₁₁ N = 169.22) Sub 2-2 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 2-3 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 2-4 _{m / z = 245.12 (C 18} H 15 N = 245.32) Sub 2-5 m / z = 170.08 (C ₁₁ H ₁₀ N ₂ = 170.21) Sub 2-6 _{m / z = 199.10 (C 10} H 13 NO = 199.25) Sub 2-7 m / z = 225.15 (C ₁₆ H ₁₉ N = 225.33) Sub 2-8 _{m / z = 285.15 (C 21} H 19 N = 285.38) Sub 2-9 m / z = 409.18 (C ₃₁ H ₂₃ N = 409.52) Sub 2-10 m / z = 407.17 (C ₃₁ H ₂₁ N = 407.51) Sub 2-11 _{m / z = 269.12 (C 20} H 15 N = 269.34) Sub 2-12 _{m / z = 269.12 (C 20} H 15 N = 269.34) Sub 2-13 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 2-14 _{m / z = 220.10 (C 15} H 12 N 2 = 220.27) Sub 2-15 _{m / z = 249.12 (C 17} H 12 NO = 249.31) Sub 2-16 m / z = 275.17 (C ₂₀ H ₂₁ N = 275.39) Sub 2-17 _{m / z = 335.17 (C 25} H 21 N = 335.44) Sub 2-18 _{m / z = 459.20 (C 35} H 25 N = 459.58) Sub 2-19 _{m / z = 457.18 (C 35} H 23 N = 457.56) Sub 2-20 _{m / z = 269.12 (C 20} H 15 N = 269.34) Sub 2-21 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 2-22 _{m / z = 220.10 (C 15} H 2 N 2 = 220.27) Sub 2-23 _{m / z = 249.12 (C 17} H 15 NO = 249.31) Sub 2-24 m / z = 275.17 (C ₂₀ H ₂₁ N = 275.39) Sub 2-25 _{m / z = 335.17 (C 25} H 21 N = 335.44) Sub 2-26 _{m / z = 459.20 (C 35} H 25 N = 459.58) Sub 2-27 _{m / z = 457.18 (C 35} H 23 N = 457.56) Sub 2-28 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 2-29 _{m / z = 246.12 (C 17} H 14 N 2 = 246.31) Sub 2-30 _{m / z = 275.13 (C 19} H 17 NO = 275.34) Sub 2-31 _{m / z = 301.18 (C 22} H 23 N = 301.42) Sub 2-32 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.48) Sub 2-33 _{m / z = 485.21 (C 37} H 27 N = 485.62) Sub 2-34 _{m / z = 483.20 (C 37} H 25 N = 483.60) Sub 2-35 _{m / z = 171.08 (C 10} H 09 N 3 = 171.20) Sub 2-36 m / z = 200.09 (C ₁₂ H ₁₂ N ₂ O = 200.24) Sub 2-37 _{m / z = 226.15 (C 15} H 18 N 2 = 226.32) Sub 2-38 _{m / z = 286.15 (C 20} H 18 N 2 = 286.37) Sub 2-39 _{m / z = 410.18 (C 30} H 22 N 2 = 410.51) Sub 2-40 _{m / z = 408.16 (C 30} H 20 N 2 = 408.49) Sub 2-41 _{m / z = 229.11 (C 14} H 15 NO 2 = 229.27) Sub 2-42 _{m / z = 255.16 (C 17} H 21 NO = 255.35) Sub 2-43 _{m / z = 315.16 (C 22} H 21 NO = 315.41) Sub 2-44 m / z = 439.19 (C ₃₂ H ₂₅ NO = 439.55) Sub 2-45 m / z = 437.18 (C ₃₂ H ₂₃ NO = 437.53) Sub 2-46 m / z = 281.21 (C ₂₀ H ₂₇ N = 281.44) Sub 2-47 _{m / z = 341.21 (C 25} H 27 N = 341.49) Sub 2-48 _{m / z = 465.25 (C 35} H 31 N = 465.63) Sub 2-49 _{m / z = 463.23 (C 35} H 29 N = 463.61) Sub 2-50 _{m / z = 401.21 (C 30} H 27 N = 401.54) Sub 2-51 m / z = 525.25 (C ₄₀ H ₃₁ N = 525.68) Sub 2-52 m / z = 523.23 (C ₄₀ H ₂₉ N = 523.66) Sub 2-53 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.46) Sub 2-54 _{m / z = 401.12 (C 28} H 19 NS = 401.52) Sub 2-55 m / z = 357.11 (C ₂₆ H ₁₇ NS = 375.48) Sub 2-56 _{m / z = 427.14 (C 30} H 21 NS = 427.56) Sub 2-57 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 2-58 _{m / z = 385.15 (C 28} H 19 NO = 385.46) Sub 2-59 m / z = 349.11 (C ₂₄ H ₁₅ NO ₂ = 349.38) Sub 2-60 m / z = 381.06 (C ₂₄ H ₁₅ NS ₂ = 381.51) Sub 2-61 m / z = 365.09 (C ₂₄ H ₁₅ NOS = 365.45) Sub 2-62 m / z = 533.13 (C ₃₆ H ₂₃ NS ₂ = 533.70) Sub 2-63 _{m / z = 501.17 (C 36} H 23 NO 2 = 501.57) Sub 2-64 m / z = 517.15 (C ₃₆ H ₂₃ NOS = 349.38)

Synthesis of Final Products

Examples of synthesis of 1-5 '

Sub 2-2 (7.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol) and P (t-Bu) ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) were added to the solution, and the mixture was refluxed at 100 ° C for 24 hours. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.8 g (yield: 85%) of final compound.

Synthesis example of 1-14 '

Sub 1-1-4 (11.4 g, 24 mmol) was dissolved in toluene, Sub 2-13 (5.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) %).

Examples of synthesis of 1-36 '

Sub 1-1-2 (9.6 g, 24 mmol) was dissolved in toluene followed by Sub 2-53 (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, _{) 3 (0.2 g, 2 mmol} ), NaO t -Bu (5.8 g, 60 mmol), toluene (300 mL) to final compounds using the respective addition of a back, the 1-5 'synthesis 13.3g (yield: 83%).

Synthesis example of 1-46 '

Sub 1-9 (7.7 g, 24 mmol) was dissolved in toluene followed by Sub 2-58 (7.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) 80%).

Synthesis example of 1-56 '

Sub 1-10 (9.6 g, 24 mmol) was dissolved in toluene and Sub 2-61 (7.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) 77%).

Synthetic example of 2-5 '

Sub 1-6 (9.6 g, 24 mmol) was dissolved in toluene followed by Sub 2-32 (7.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) were added to the solution, and the mixture was refluxed at 100 ° C for 24 hours. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 13.2 g (yield: 81%) of final compound.

Synthetic examples of 2-10 '

Sub 1-18 (9.6 g, 24 mmol) was dissolved in toluene followed by Sub 2-28 (6.4 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) were added, 78%).

Synthesis example of 2-14 '

Sub 1-1-8 (11.4 g, 24 mmol) was dissolved in toluene and Sub 2-13 (5.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) 83%).

Synthesis Example of 2-36 '

Sub 1-6 (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol) and P (t-Bu ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) 78%).

Synthesis Example of 2-46 '

Sub 1- 12 (7.7 g, 24 mmol) was dissolved in toluene followed by Sub 2-58 (7.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) %).

Synthetic example of 2-56 '

Sub 3-1-13 (9.6 g, 24 mmol) was dissolved in toluene followed by Sub 2-61 (7.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, ), ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (300 mL) 75%).

The obtained product was confirmed by Mass Data as follows.

compound FD-MS compound FD-MS 1-1 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 1-2 ' m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) 1-3 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 1-4 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 1-5 ' m / z = 678.30 (C ₄₂ H ₃₈ N ₂ = 678.86) 1-6 ' m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) 1-7 ' m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) 1-8 ' m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) 1-9 ' m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) 1-10 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 1-11 ' m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) 1-12 ' m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) 1-13 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 1-14 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 1-15 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86)) 1-16 ' m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) 1-17 ' m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) 1-18 ' m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) 1-19 ' m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) 1-20 ' m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) 1-21 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 1-22 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 1-23 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 1-24 ' m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) 1-25 ' m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 1-26 ' m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) 1-27 ' m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) 1-28 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 1-29 ' m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) 1-30 ' m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) 1-31 ' m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) 1-32 ' m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) 1-33 ' m / z = 592.20 (C ₄₂ H ₂₈ N ₂ S = 592.75) 1-34 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 1-35 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 1-36 ' m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 1-37 ' m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 1-38 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 1-39 ' m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) 1-40 ' m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) 1-41 ' m / z = 576.22 (C ₄₂ H ₂₈ N ₂ O = 576.22) 1-42 ' m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) 1-43 ' m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) 1-44 ' m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 1-45 ' m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 1-46 ' m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) 1-47 ' m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) 1-48 ' m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) 1-49 ' m / z = 622.15 (C ₄₂ H ₂₆ N ₂ S ₂ = 622.80) 1-50 ' m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S ₂ = 698.90) 1-51 ' m / z = 850.25 (C ₆₀ H ₃₈ N ₂ S ₂ = 851.09) 1-52 ' m / z = 804.17 (C ₅₄ H ₃₂ N ₂ S ₃ = 805.04) 1-53 ' m / z = 606.18 (C ₄₂ H ₂₆ N ₂ OS = 606.73) 1-54 ' m / z = 682.21 (C ₄₈ H ₃₀ N ₂ OS = 682.83) 1-55 ' m / z = 834.27 (C ₆₀ H ₃₈ N ₂ OS = 835.02) 1-56 ' m / z = 683.20 (C ₄₇ H ₂₉ N ₃ OS = 683.82) 2-1 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 2-2 ' m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) 2-3 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 2-4 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 2-5 ' m / z = 678.30 (C ₄₂ H ₃₈ N ₂ = 678.86) 2-6 ' m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) 2-7 ' m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) 2-8 ' m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) 2-9 ' m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) 2-10 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 2-11 ' m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) 2-12 ' m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) 2-13 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 2-14 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 2-15 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86)) 2-16 ' m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) 2-17 ' m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) 2-18 ' m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) 2-19 ' m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) 2-20 ' m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) 2-21 ' m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 2-22 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 2-23 ' m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 2-24 ' m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) 2-25 ' m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 2-26 ' m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) 2-27 ' m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) 2-28 ' m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) 2-29 ' m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) 2-30 ' m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) 2-31 ' m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) 2-32 ' m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) 2-33 ' m / z = 592.20 (C ₄₂ H ₂₈ N ₂ S = 592.75) 2-34 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 2-35 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 2-36 ' m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 2-37 ' m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 2-38 ' m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) 2-39 ' m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) 2-40 ' m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) 2-41 ' m / z = 576.22 (C ₄₂ H ₂₈ N ₂ O = 576.22) 2-42 ' m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) 2-43 ' m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) 2-44 ' m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 2-45 ' m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 2-46 ' m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) 2-47 '' m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) 2-48 ' m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) 2-49 ' m / z = 622.15 (C ₄₂ H ₂₆ N ₂ S ₂ = 622.80) 2-50 ' m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S ₂ = 698.90) 2-51 ' m / z = 850.25 (C ₆₀ H ₃₈ N ₂ S ₂ = 851.09) 2-52 ' m / z = 804.17 (C ₅₄ H ₃₂ N ₂ S ₃ = 805.04) 2-53 ' m / z = 606.18 (C ₄₂ H ₂₆ N ₂ OS = 606.73) 2-54 ' m / z = 682.21 (C ₄₈ H ₃₀ N ₂ OS = 682.83) 2-55 ' m / z = 834.27 (C ₆₀ H ₃₈ N ₂ OS = 835.02) 2-56 ' m / z = 683.20 (C ₄₇ H ₂₉ N ₃ OS = 683.82)

Evaluation of manufacturing of organic electric device

[Example I-1] Blue organic electroluminescent device (hole transport layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") was vacuum deposited on the ITO layer (anode) To form a hole injection layer, and then the mixture of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Subsequently, a light emitting layer with a thickness of 30 nm was deposited on the hole transport layer by doping 9,10-di (naphthalen-2-yl) anthracene on the hole transport layer and BD-052X (Idemitsukosan) as a dopant. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light emitting layer to a thickness of 10 nm (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transporting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[Comparative Example 1]

An organic electroluminescence device was fabricated in the same manner as in Example I-1, except that the following Comparative Compound 1 was used instead of the mixture of the present invention as the hole transport layer material.

[Comparative Example 2]

An organic electroluminescence device was fabricated in the same manner as in Example I-1 except that the compound of the present invention was used alone as a hole transport layer material instead of the compound of the present invention.

[Comparative Example 3]

An organic electroluminescent device was fabricated in the same manner as in Example I-1, except that the compound of the present invention was used alone as a hole transport layer material instead of the compound of the present invention.

Electroluminescence (EL) characteristics of organic electroluminescent devices manufactured by the above-described Examples and Comparative Examples 1 to 3 were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by the above- Measurement results The T95 lifetime was measured at a luminance of 500 cd / m 2 through a life measuring device manufactured by Mac Science. The following table shows the results of device fabrication and evaluation.

Mixing ratio Compound A Compound B Driving
Voltage electric current
(mA / cm 2) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) Luminous color T (95) Comparative Example (1) Single compound Comparative Compound (1) none 4.5 15.2 500.0 3.3 blue 83.0 Comparative Example (2) Single compound Compound 1-4 none 4.1 10.6 500.0 4.7 blue 105.5 Comparative Example (3 Single compound Compound 2-10 none 4.3 11.1 500.0 4.5 blue 102.7 Example (1) A (2): B (8) The compound 1-4 ' Compound 1-1 ' 4.1 8.7 500.0 5.7 blue 117.4 Example (2) A (2): B (8) The compound 1-4 ' Compound 1-12 ' 4.1 8.9 500.0 5.6 blue 118.0 Example (3) A (2): B (8) The compound 1-4 ' Compound 1-28 ' 4.1 9.3 500.0 5.4 blue 120.9 Example (4) A (2): B (8) The compound 1-4 ' Compound 1-36 ' 4.1 9.0 500.0 5.5 blue 111.6 Example (5) A (2): B (8) The compound 1-4 ' Compound 1-44 ' 4.0 9.1 500.0 5.5 blue 118.1 Example (6) A (2): B (8) The compound 1-4 ' Compound 2-2 ' 4.0 8.9 500.0 5.6 blue 114.0 Example (7) A (2): B (8) The compound 1-4 ' Compound 2-16 ' 4.1 9.3 500.0 5.4 blue 119.5 Example (8) A (2): B (8) The compound 1-4 ' Compound 2-27 ' 4.1 8.9 500.0 5.6 blue 122.9 Example (9) A (2): B (8) The compound 1-4 ' Compound 2-36 ' 4.2 8.9 500.0 5.6 blue 111.8 Example (10) A (2): B (8) Compound 2-10 ' Compound 2-2 ' 4.0 8.7 500.0 5.8 blue 127.2 Example (11) A (2): B (8) Compound 2-10 ' Compound 2-16 ' 4.0 9.4 500.0 5.3 blue 118.8 Example (12) A (2): B (8) Compound 2-10 ' Compound 2-27 ' 4.0 8.6 500.0 5.8 blue 125.5 Example (13) A (2): B (8) Compound 2-10 ' Compound 2-36 ' 4.1 8.7 500.0 5.8 blue 115.6 Example (14) A (3): B (7) The compound 1-4 ' Compound 1-1 ' 4.0 8.7 500.0 5.7 blue 113.8 Example (15) A (3): B (7) The compound 1-4 ' Compound 1-12 ' 4.1 9.2 500.0 5.4 blue 116.6 Example (16) A (3): B (7) The compound 1-4 ' Compound 1-28 ' 4.2 8.7 500.0 5.7 blue 116.2 Example (17) A (3): B (7) The compound 1-4 ' Compound 1-36 ' 4.1 9.0 500.0 5.5 blue 121.5 Example (18) A (3): B (7) The compound 1-4 ' Compound 1-44 ' 4.2 9.2 500.0 5.4 blue 126.9 Example (19) A (3): B (7) The compound 1-4 ' Compound 2-2 ' 4.1 8.7 500.0 5.7 blue 121.1 Example (20) A (3): B (7) The compound 1-4 ' Compound 2-16 ' 4.2 9.3 500.0 5.4 blue 111.8 Example (21) A (3): B (7) The compound 1-4 ' Compound 2-27 ' 4.1 8.7 500.0 5.8 blue 119.1 Example (22) A (3): B (7) The compound 1-4 ' Compound 2-36 ' 4.1 9.3 500.0 5.4 blue 125.5 Example (23) A (3): B (7) Compound 2-10 ' Compound 2-2 ' 4.1 9.3 500.0 5.4 blue 122.3 Example (24) A (3): B (7) Compound 2-10 ' Compound 2-16 ' 4.2 8.9 500.0 5.6 blue 124.6 Example (25) A (3): B (7) Compound 2-10 ' Compound 2-27 ' 4.0 8.7 500.0 5.8 blue 125.3 Example (26) A (3): B (7) Compound 2-10 ' Compound 2-36 ' 4.0 9.2 500.0 5.5 blue 113.3 Example (27) A (4): B (6) The compound 1-4 ' Compound 1-1 ' 4.2 9.3 500.0 5.4 blue 111.7 Example (28) A (4): B (6) The compound 1-4 ' Compound 1-12 ' 4.2 9.3 500.0 5.4 blue 119.0 Example (29) A (4): B (6) The compound 1-4 ' Compound 1-28 ' 4.1 9.3 500.0 5.4 blue 128.5 Example (30) A (4): B (6) The compound 1-4 ' Compound 1-36 ' 4.1 8.8 500.0 5.7 blue 117.4 Example (31) A (4): B (6) The compound 1-4 ' Compound 1-44 ' 4.1 8.7 500.0 5.8 blue 114.8 Example (32) A (4): B (6) The compound 1-4 ' Compound 2-2 ' 4.1 9.4 500.0 5.3 blue 123.6 Example (33) A (4): B (6) The compound 1-4 ' Compound 2-16 ' 4.2 9.3 500.0 5.4 blue 124.5 Example (34) A (4): B (6) The compound 1-4 ' Compound 2-27 ' 4.1 9.3 500.0 5.4 blue 120.1 Example (35) A (4): B (6) The compound 1-4 ' Compound 2-36 ' 4.2 8.9 500.0 5.6 blue 116.9 Example (36) A (4): B (6) Compound 2-10 ' Compound 2-2 ' 4.2 9.2 500.0 5.5 blue 110.3 Example (37) A (4): B (6) Compound 2-10 ' Compound 2-16 ' 4.2 9.1 500.0 5.5 blue 119.3 Example (38) A (4): B (6) Compound 2-10 ' Compound 2-27 ' 4.2 8.8 500.0 5.7 blue 115.2 Example (39) A (4): B (6) Compound 2-10 ' Compound 2-36 ' 4.1 8.7 500.0 5.8 blue 113.2 Example (40) A (5): B (5) The compound 1-4 ' Compound 1-1 ' 3.9 9.0 500.0 5.6 blue 124.9 Example (41) A (5): B (5) The compound 1-4 ' Compound 1-12 ' 4.0 8.4 500.0 5.9 blue 123.1 Example (42) A (5): B (5) The compound 1-4 ' Compound 1-28 ' 4.0 8.5 500.0 5.9 blue 126.3 Example (43) A (5): B (5) The compound 1-4 ' Compound 1-36 ' 3.9 8.5 500.0 5.9 blue 126.1 Example (44) A (5): B (5) The compound 1-4 ' Compound 1-44 ' 4.0 8.5 500.0 5.9 blue 128.4 Example (45) A (5): B (5) The compound 1-4 ' Compound 2-2 ' 3.9 8.4 500.0 5.9 blue 123.7 Example (46) A (5): B (5) The compound 1-4 ' Compound 2-16 ' 4.0 8.4 500.0 5.9 blue 116.1 Example (47) A (5): B (5) The compound 1-4 ' Compound 2-27 ' 4.0 8.5 500.0 5.9 blue 122.0 Example (48) A (5): B (5) The compound 1-4 ' Compound 2-36 ' 4.0 8.5 500.0 5.9 blue 110.8 Example (49) A (5): B (5) Compound 2-10 ' Compound 2-2 ' 4.0 8.4 500.0 6.0 blue 112.7 Example (50) A (5): B (5) Compound 2-10 ' Compound 2-16 ' 3.9 8.3 500.0 6.0 blue 124.2 Example (51) A (5): B (5) Compound 2-10 ' Compound 2-27 ' 3.9 8.5 500.0 5.9 blue 124.9 Example (52) A (5): B (5) Compound 2-10 ' Compound 2-36 ' 3.9 8.4 500.0 6.0 blue 117.5 Example (53) A (7): B (3) The compound 1-4 ' Compound 1-1 ' 4.1 8.7 500.0 5.8 blue 123.1 Example (54) A (7): B (3) The compound 1-4 ' Compound 1-12 ' 4.1 9.4 500.0 5.3 blue 124.6 Example (55) A (7): B (3) The compound 1-4 ' Compound 1-28 ' 4.2 8.8 500.0 5.7 blue 113.3 Example (56) A (7): B (3) The compound 1-4 ' Compound 1-36 ' 4.1 9.1 500.0 5.5 blue 123.0 Example (57) A (7): B (3) The compound 1-4 ' Compound 1-44 ' 4.0 8.9 500.0 5.6 blue 117.3 Example (58) A (7): B (3) The compound 1-4 ' Compound 2-2 ' 4.2 9.4 500.0 5.3 blue 122.8 Example (59) A (7): B (3) The compound 1-4 ' Compound 2-16 ' 4.0 8.8 500.0 5.7 blue 115.2 Example (60) A (7): B (3) The compound 1-4 ' Compound 2-27 ' 4.1 9.2 500.0 5.5 blue 110.7 Example (61) A (7): B (3) The compound 1-4 ' Compound 2-36 ' 4.1 8.8 500.0 5.7 blue 128.2 Example (62) A (7): B (3) Compound 2-10 ' Compound 2-2 ' 4.1 9.1 500.0 5.5 blue 113.1 Example (63) A (7): B (3) Compound 2-10 ' Compound 2-16 ' 4.1 9.4 500.0 5.3 blue 112.1 Example (64) A (7): B (3) Compound 2-10 ' Compound 2-27 ' 4.1 8.9 500.0 5.6 blue 129.1 Example (65) A (7): B (3) Compound 2-10 ' Compound 2-36 ' 4.2 9.3 500.0 5.4 blue 122.1 Example (66) A (5): B (5) Compound 1-44 ' Compound 1-1 ' 3.9 8.1 500.0 6.2 blue 120.9 Example (67) A (5): B (5) Compound 1-44 ' Compound 1-36 ' 3.9 7.8 500.0 6.5 blue 124.9 Example (68) A (5): B (5) Compound 1-44 ' Compound 1-44 ' 3.9 8.0 500.0 6.3 blue 124.8 Example (69) A (5): B (5) Compound 1-44 ' Compound 2-2 ' 3.8 7.8 500.0 6.4 blue 119.0 Example (70) A (5): B (5) Compound 1-44 ' Compound 2-16 ' 3.8 7.9 500.0 6.3 blue 111.3 Example (71) A (5): B (5) Compound 1-44 ' Compound 2-27 ' 3.8 8.1 500.0 6.1 blue 119.2 Example (72) A (5): B (5) Compound 1-44 ' Compound 2-36 ' 3.9 8.1 500.0 6.2 blue 129.4 Example (73) A (5): B (5) Compound 2-45 ' Compound 1-1 ' 3.9 7.8 500.0 6.4 blue 120.3 Example (74) A (5): B (5) Compound 2-45 ' Compound 1-36 ' 3.9 7.9 500.0 6.3 blue 116.8 Example (75) A (5): B (5) Compound 2-45 ' Compound 1-44 ' 3.9 8.0 500.0 6.2 blue 122.9 Example (76) A (5): B (5) Compound 2-45 ' Compound 2-2 ' 3.9 7.9 500.0 6.3 blue 128.5 Example (77) A (5): B (5) Compound 2-45 ' Compound 2-16 ' 3.8 8.0 500.0 6.3 blue 115.3 Example (78) A (5): B (5) Compound 2-45 ' Compound 2-27 ' 3.9 7.7 500.0 6.5 blue 123.1 Example (79) A (5): B (5 Compound 2-45 ' Compound 2-36 ' 3.8 8.1 500.0 6.2 blue 120.7

As can be seen from the results of the above table, when the mixture of the present invention is used as a hole transporting layer, it can be confirmed that it has higher efficiency and longer lifetime than Comparative Examples 1 to 3 using a single compound.

The results of the above table are described in more detail. The compounds represented by the formula (1) were added to each other at a ratio of 2: 8 (molar ratio) to the compounds of the comparative examples 2 and 3 which used the compounds 1-4 'and 2-10' , 3: 7, 5: 5, and 7: 3 as the hole transport layer, the efficiency and lifetime of Examples 1 to 79 were higher than those of Comparative Examples, and the driving voltage was also similar or decreased.

As a result of proceeding from Examples 1 to 79, it was confirmed that the mixing efficiency was 5: 5, which indicates the highest efficiency increase and the life span increase. Therefore, when the mixing ratio is limited to 5: 5 and 1-44 'and 2-45' in which the heterocyclic group is substituted among the compounds represented by the compound 1 are mixed with other compounds represented by the compound 1 to measure the device, The results of the device in which Dibenzofuran or Dibenzothiophen substituted 1-44 ', 2-45' with other compounds represented by Compound 1 were found to result in 1-4 ', 2-10' I could confirm that it was better.

That is, when the two compounds represented by the formula (1) were mixed and used in the hole transport layer, it was confirmed that the lifetime and efficiency were superior to those in the case of using a single compound, and the results of the device were slightly different The results of the device with the mixing ratio of 5: 5 were the best. This proves that the present invention is more advanced than an example using a conventional single compound as a hole transport layer.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: First electrode (anode) 130: Hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)

Claims (16)

A first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound,
Wherein the hole transport layer is composed of a composition in which two kinds of carbazole compounds differing in structure are mixed, and a compound ratio of each of the different structural formulas is selected from 5: 5 to 9: 1. A first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer comprises a compound represented by the following formula The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device

Wherein Ar ¹ to Ar ³ are each independently selected from the group consisting of an aryl group having _{6 to 60} carbon atoms, a heteroaryl group having _{2 to 60} carbon atoms, and a fluorenyl group,
L ¹ is a single bond, C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60} of the heterocyclic group, fluorenyl group, a divalent fused ring of an aromatic ring of C _{3 ~ 60} alicyclic and C _{6 to 60} of Group, &lt; / RTI &gt;
m is selected from integers of 0 to 4, n is selected from integers of 0 to 3,
R ^{1 and} R ² are the same as or different from each other, and are independently selected from the group consisting of deuterium; Tritium; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; Is selected from the group consisting of; and O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of the P
When m and n are two or more, R ^{1 to} R ² are the same or different from each other, and a plurality of R ^{1 s} or a plurality of R ^{2 s} may combine with each other to form a ring.
A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -L _{'-N (R a) (R} b); C 1 ~ Import alkylthio of C _20; C ₁ ~ alkoxy group of C _20; C ₁ ~ alkyl group of C _20; C ₂ ~ C ₂₀ alkenyl group a; ₂ C ~ alkynyl of C _20; an aryl group of C ₆ - C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; C ₂ - heterocyclic group of C _20; C of ₃ ~ C ₂₀ cycloalkyl An alkyl group, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term &quot; ring &quot; means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)} The organic electroluminescent device according to claim 2, wherein the compound represented by the formula (1) is one of the following formula (1-1) or (1-2)

(Wherein Ar ^1-3 , L ¹ , R ¹ , R ² , m and n are the same as defined in claim 2). 3. The method of claim 2,
The organic electroluminescent device according to claim 1, wherein the compound represented by Formula 1 is represented by the following Formulas 1-3, 1-4, 1-5,

(Wherein Ar ¹ , Ar ² , R ¹ , R ² , L ¹ , m and n are the same as defined in claim 2,
V and W are each independently S, O or CR'R ", and R 'and R" are each independently a C _6-24 aryl group, a C _1-20 alkyl group, a C _2-20 alkenyl or C _{A 1-20} alkoxy group; R 'and R "may combine to form a spy,
R ³ ~ R ⁶ are each independently selected from deuterium, tritium, a cyano group, a group, a halogen group, an aryl group, an alkenyl group, an alkylene group, an alkoxy group, a hetero group, ring, nitro, R ³ together, R ⁴ , R ⁵ and R ^{6 may} be bonded together to form a ring, a and o represent an integer of 0-3, and b and p represent an integer of 0-4. 3. The method of claim 2,
The organic electroluminescent device according to claim 1, wherein the compound represented by Formula 1 is represented by the following formula

3. The method of claim 2,
Wherein Ar ¹ , Ar ² , and Ar ³ of the ^two compounds represented by Formula 1 are all C _{6 to} C ₂₄ aryl groups. 3. The method of claim 2,
Ar ¹ , Ar ² , and Ar ³ of one of the two compounds represented by Formula 1 are all C _{6 to} C ₂₄ aryl groups; Wherein at least one of Ar ¹ , Ar ² and Ar ³ of the remaining one kind of compound is dibenzothiophene or dibenzofuran. 3. The method of claim 2,
Wherein at least one of Ar ¹ , Ar ² , and Ar ³ of the ^two compounds represented by Formula 1 is dibenzothiophene or dibenzofuran, 3. The method of claim 2,
Wherein the weight ratio of any one of the two kinds of compounds having different structures represented by the formula (1) is 10% to 90%. 3. The method of claim 2,
Wherein the mixing ratio is 5: 5 or 6: 4 or 7: 3, or 8: 2 or 9: 1 when two compounds having different structures represented by the formula (1) are mixed. Electric device. 3. The method of claim 2,
Wherein the organic electroluminescent device further comprises at least one compound represented by the general formula (1) in a composition in which the compounds represented by the general formula (1) are different from each other. 3. The method of claim 2,
Wherein the compound represented by Chemical Formula 1 is used as a luminescent auxiliary layer between a hole transporting layer containing a composition of two kinds of compounds having different structures represented by Chemical Formula 1 and a light emitting layer. 3. The method of claim 2,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer. 3. The method of claim 2,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device according to claim 2; And a controller for driving the display device. &Lt; / RTI &gt; 16. The method of claim 15,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor and a monochromatic or white illumination device.

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