KR20160113783A - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

Provided is a compound represented by chemical formula 1. Also, provided is an organic electric device including a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode. The organic layer includes the compound represented by chemical formula 1. An organic electric device having an organic layer including the compound represented by chemical formula 1 has reduced operating voltage, and enhanced luminous efficiency, color purity, lifespan, and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

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 longevity are also important factors to be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, Indicating a tendency for the lifetime to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and the T ₁ value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

In recent years, in order to solve the emission problem and the driving voltage problem in the hole transport layer in the organic electroluminescent device, it is necessary that the emission auxiliary layer (multilayered hole transport layer) be present between the hole transport layer and the light emitting layer, It is time to develop an auxiliary layer.

Generally, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to recombine in the light emitting layer to form excitons. However, when a material having a high hole mobility is used to form a low driving voltage, a positive polaron is accumulated at the interface between the light emitting layer and the hole transporting layer, thereby causing interface deterioration, thereby reducing the lifetime and efficiency , And the charge balance in the light emitting layer does not match, so that the excess Polaron in the light emitting layer attacks the weak bonding of the light emitting material, and the light emitting material is deformed, so that the lifetime, efficiency and color purity decrease have.

Therefore, the luminescent auxiliary layer exists between the hole transporting layer and the luminescent layer and must have a proper HOMO value between the luminescent layer and the hole transporting layer in order to prevent the positive polaron from accumulating at the interface of the luminescent layer. (Within the ble device driving voltage range of the full device) within a reasonable driving voltage range to increase the voltage, current, and balance.

However, this can not be achieved simply by the structural characteristics of the core of the light-emitting auxiliary layer material, and when the proper combination of the characteristics of the core and the sub-substituent of the light-emitting auxiliary layer material and the light emitting auxiliary layer, the hole transport layer, High efficiency and high number of devices can be realized.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, The material to be supported by the material should be preceded and development of materials for the light emitting auxiliary layer and the hole transporting layer is desperately required.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a compound having efficient electron blocking ability and hole transporting ability, , Color purity and lifetime, and an organic electronic device using the compound and an electronic device thereof.

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

≪ Formula 1 >

In another aspect, the present invention provides an organic electronic device using the compound represented by Formula 1 and an electronic device thereof.

By using the compound of the present invention as a material for an organic electric device, it is possible to improve the luminous efficiency, heat resistance, color purity, lifetime, and the like of the organic electric device due to the HOMO energy level and the high T ₁ value, And the driving voltage can be lowered.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

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

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals whenever possible, even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can 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."

In addition, when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, And the like. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

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 "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, It is not.

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.

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 term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R 'and R & Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R 'and R" is a substituent other than hydrogen, and R and R' Together with a spy compound.

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, the aryl group or the arylene group includes a single ring, a ring group, a plurality of ring systems bonded together, a spiro compound and the like.

The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group ", but also nonaromatic rings, Means a ring of 2 to 60 rings, but is not limited thereto. The term "heteroatom ", as used herein, unless otherwise indicated, refers to N, O, S, P, or Si, wherein the heterocyclic group includes single ring, ring, And the like.

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.

The term "divalent benzothiophene" as used herein means a divalent functional group of the parent compound benzothiophene, and similarly, "divalent dibenzothiophene" Quot; bivalent furane "refers to the bivalent functional group of the parent compound furan," divalent dibenzofuran "refers to the divalent functional group of the dibenzofurane, which is the parent compound, and" divalent pyrimidine & Means a divalent functional group of pyrimidine. That is, in the present specification, when naming the divalent functional group of the parent compound, the divalent functional group may be simply referred to as a divalent compound in front of the parent compound.

As used herein, the term "ring" includes monocyclic and polycyclic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom and including aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, and the like, as well as various fused ring systems and spiro compounds, including aromatic as well as non- The ring includes, of course, a heterocycle containing at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (a single ring or a fused ring system) are directly connected to each other through a single bond or a double bond, Means that the number of linkages is one less than the total number of rings in the compound. The ring assemblies may be directly connected to each other through a single bond or a double bond.

As used herein, the term " conjugated ring system "refers to a fused ring form shared by at least two atoms, in which the ring system of two or more hydrocarbons is conjugated and contains at least one heteroatom And at least one hetero ring system bonded thereto. Such conjugated ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and a spiro connection means a connection in which two rings share only one atom. At this time, atoms shared in two rings are called 'spyro atoms', and they are referred to as 'monospyros,' 'di spyroses,' and 'tri-spyros', depending on the number of spyro atoms contained in a compound. 'Compounds.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. Means, for example, an alkoxy group substituted with an aryl group in the case of an arylalkoxy group, a carbonyl group substituted with an alkoxy group in the case of an alkoxycarbonyl group, and an alkenyl group substituted with an arylcarbonyl group in the case of an arylcarbonylalkenyl group, The arylcarbonyl group is a carbonyl group substituted with an aryl group.

In addition, a no explicit description, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro _{group, C 1 -C 20, C 1} -C 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, C ₂ -C of ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron And a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, with the proviso that at least one substituent And is not limited to these substituents.

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.

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

1, an organic electroluminescent device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 formed on a substrate 110, And an organic material layer containing a compound according to the present invention is provided between the two electrodes 180. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, etc., and the electron transporting layer 160 may serve as a hole blocking layer You can do it.

Also, although not shown, the organic electroluminescent device according to an embodiment of the present invention further includes a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer can do.

The compound according to one embodiment of the present invention applied to the organic material layer may be a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, It may be used as a material for the light-efficiency improvement layer. For example, the compound of the present invention can be used as a material for the light emitting layer 150, the hole transporting layer 140 and / or the light emitting auxiliary layer 151, and preferably the material for the hole transporting layer 140 and / .

On the other hand, even if the core is the same core, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at which position, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T ₁ value between the organic layers, and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time.

As described above, in order to solve the problem of light emission in the hole transporting layer in an organic electroluminescent device, it is preferable that a light-emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer. It is necessary to develop different light-emitting auxiliary layers according to the above.

On the other hand, in the case of the light-emission-assisting layer, it is difficult to deduce the characteristics of the organic layer to be used even if a similar core is used because the relationship between the hole-transport layer and the light-emitting layer (host)

Therefore, in the present invention, by forming the hole transporting layer and / or the light-emitting auxiliary layer by using the compound represented by the general formula (1), the energy level and T ₁ value between each organic material layer, the intrinsic properties (mobility, The lifetime and the efficiency of the organic electronic device can be improved at the same time.

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. For example, a metal or a metal oxide having conductivity or an alloy thereof may be deposited on a substrate to form a cathode 120, and a hole injection layer 130 may be formed thereon. A hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170, and then depositing a material that can be used as a cathode 180 on the organic layer. have. Further, a light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

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

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or a device for monochromatic or white illumination.

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

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

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

≪ Formula 1 >

Each symbol in the above formula (1) is defined as follows.

Ar ¹ to Ar ⁴ independently represent C ₆ -C ₆₀ An aryl group; A fluorenyl group; O, N, S, Si, and P, and at least one heteroatom selected from the group consisting of C ₂ -C ₆₀ A heterocyclic group; C ₁ -C ₆₀ An alkyl group; And C ₆ -C ₆₀ Aromatic rings and C ₃ -C ₆₀ And a fused ring group of an aliphatic ring.

Aryl groups preferably, Ar ¹ to Ar ⁴ is independently C ₆ -C ₆₀ with each other; A fluorenyl group; O, N, S, Si, and P, and at least one heteroatom selected from the group consisting of C ₂ -C ₆₀ A heterocyclic group and the like, and also preferably a C ₆ -C ₁₈ aryl group; A fluorenyl group; Or a C ₂ -C ₁₆ heterocyclic group containing at least one hetero atom selected from O, N, and S.

; 페닐로 치환되거나 비치환된 인돌릴기; 피리딜기, 피리딜기로 치환되거나 비치환된 피리미딜기; 또는 페닐로 치환되거나 비치환된 카바졸릴기일 수 있다.More preferably, Ar ¹ to Ar ⁴ are each independently a heavy hydrogen, fluorine group, a phenyl group, a naphthyl group, a methyl group, tert - butyl, ethene group, a 9,9-dimethyl -9 H - fluorene group, a pyridyl group, A dibenzothienyl group, a carbazolyl group, or a phenyl substituted or unsubstituted with a methoxyl group; Biphenyl unsubstituted or substituted with deuterium or phenyl; Naphthyl which is unsubstituted or substituted with phenyl or pyridyl groups; A phenanthryl group; A terphenyl group; 9,9-dimethyl -9 H - fluorenyl group; 11,11- dimethyl -11 H - benzo [b] fluorene group; 9,9-diphenyl -9 H - fluorenyl group; A 9,9'-spirobifluorenyl group; Monovalent dibenzothiophenes substituted with phenyl (i.e., dibenzothienyl groups); A monovalent dibenzofurane (i.e., a dibenzofuryl group) substituted or unsubstituted with a methyl group;

; An indolyl group substituted or unsubstituted with phenyl; A pyridyl group, a pyrimidyl group substituted or unsubstituted with a pyridyl group; Or a carbazolyl group substituted or unsubstituted with phenyl.

When each of Ar ¹ to Ar ⁴ is an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, or an alkyl group, each of these may be deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And -LN (R ') (R ");

In this case, in the -LN (R ') (R "), L is a single bond, an arylene group, a fluorenylene group, a C ₂ -C ₆₀ alkylene group containing at least one heteroatom selected from O, N, S, A divalent heterocyclic group, and a divalent fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; and R 'and R "are each independently selected from the group consisting of C ₆ -C ₆₀ An aryl group; A fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; A C ₁ -C ₆₀ alkyl group; And a fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring.

In Formula 1, m and n are each an integer of 0 to 4, R ¹ and R ² are each independently selected from the group consisting of deuterium; Tritium; A halogen group; Cyano; A nitro group; C ₆ -C ₆₀ An aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} ~ 60 containing at least one hetero atom of Si and P; C ₆ -C ₆₀ Aromatic rings and C ₃ -C ₆₀ A fused ring group of an aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₃₀ . When m is an integer of 2 or more, a plurality of R ^{1 s} may be the same as or different from each other, and when n is an integer of 2 or more, a plurality of R ^{2 s} may be the same or different from each other.

Preferably, R ¹ and R ² independently of one another are cyano, C ₆ -C ₆₀ An aryl group, O, N, and and the like heterocyclic group of C _{2 ~ 60} containing at least one hetero atom of S, more preferably R ¹ and R ² are independently a cyano group, a phenyl group, pyridyl group or the like to each other .

Further, when m and n are each an integer of 2 or more, when a plurality of neighboring R ¹ and R ² are present, adjacent R ¹ or adjacent R ² may be bonded to each other to form a ring. Here, 'neighboring groups may combine with each other to form a ring' means that when m is 2 or more, a plurality of neighboring R ^{1 s} , when n is 2 or more, a plurality of R ^{2 s} are bonded to each other to form benzene Means that a ring can be formed together with the ring. At least one pair of adjacent groups may form a ring independently of each other. For example, at least one pair of R ¹ groups or R ² groups may form a ring, or all of these adjacent pairs may form a ring. . On the other hand, when only a part of the adjacent groups form a ring, R ¹ and R ² which do not form a ring may be selected from the substituents defined above.

The ring formed by bonding R ¹ or R ^{2 to} each other is usually a 5- to 8-membered ring, but is preferably a 5- or 6-membered ring, more preferably a 6-membered ring. In this case, the ring formed may be an aromatic ring or an aliphatic ring, and in the case of an aromatic ring, it may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring. Further, neighboring groups may be linked by alkylene or alkenylene to form an alicyclic ring, a monocyclic or polycyclic aromatic ring. Preferably, the ring formed by bonding R ¹ and R ^{2 to} each other may be a benzene ring, and together with the benzene ring to which they are bonded, naphthalene, phenanthrene, etc. may be formed.

When R ¹ and R ² are an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryloxy group, halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And -LN (R ') (R ");

In this case, in the -LN (R ') (R "), L is a single bond, an arylene group, a fluorenylene group, a C ₂ -C ₆₀ alkylene group containing at least one heteroatom selected from O, N, S, A divalent heterocyclic group, and a divalent fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; and R 'and R "are each independently selected from the group consisting of C ₆ -C ₆₀ An aryl group; A fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; A C ₁ -C ₆₀ alkyl group; And a fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring.

The formula 1 may be represented by one of the following formulas (2) to (7), and the symbols in the following formulas (2) to (7) may be defined as defined in formula (1).

Specifically, the compound represented by the formula (1) may be one of the following compounds.

In another aspect of the present invention, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer is at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer of the organic material layer, At least one may be included. That is, the organic material layer may be formed of a single species compound represented by the general formula (1) or a mixture of two or more species.

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

Synthetic example

The compounds represented by formula (1) according to the present invention can be synthesized by reacting Sub 1 and Sub 2 as in the following reaction scheme, but are not limited thereto.

I. Synthesis of Sub 1

Sub 1 of Reaction Scheme 1 can be synthesized by the following reaction formula.

1.1. Sub 1-1 synthesis example

(1) Sub 1-I-1 synthesis

To a round bottom flask was added 4-chlorophenyl boronic acid (4.5 g, 28 mmol), N-phenylnaphthalen-2-amine (6.3 g, 28 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol) Bu) ₃ (0.4 g, 1.7 mmol), NaO t- Bu (8.3 g, 86 mmol) and toluene (280 mL). 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 8.5 g of Sub 1-I-1. (Yield: 87%).

(2) Sub 1-1 Synthesis

Sub-1-I-1 (8.5 g, 25 mmol) was added to a round bottom flask and 2,3-dibromonaphthalene (8.6 g, 30 mmol), Pd (PPh ₃ ) ₄ (0.9 g, 0.8 mmol) 75 mL), THF (240 mL) and water (120 mL). Thereafter, the mixture is heated under reflux at 80 캜. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8 g of Sub 1-1. (Yield: 64%).

1.2. Sub 1-2 Composite Example

(1) Sub 1-I-2 synthesis

N-phenylphenanthren-9-amine (7.2 g, 27 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol) and P (t-Bu ) ₈ (0.3 g, 1.6 mmol), NaO t- Bu (7.7 g, 81 mmol) and toluene (270 mL) were obtained using the Sub 1-I-1 synthesis method. (Yield: 85%).

(2) Sub 1-2 synthesis

2,3-dibromonaphthalene (7.9 g, 27 mmol), Pd (PPh ₃ ) ₄ (0.8 g, 0.7 mmol) and NaOH (2.7 g, 69 mmol) were added to Sub 1-I-2 (8.9 g, , THF (250 mL), and water (125 mL). Sub-1-1 synthesis was used to obtain 8.7 g of the product. (Yield: 69%).

1.2. Sub 1-5 Synthetic Example

(1) Sub 1-I-5 synthesis

4-yl) naphthalen-1-amine (6.0 g, 21 mmol) and Pd ₂ (dba) were added to the starting material (4-chlorophenyl) boronic acid (3.2 g, 21 mmol) _{3 (0.6g, 0.6mmol), P} (t-bu) 3 (0.3g, 1.2mmol), NaO t -Bu (5.9g, 61mmol), toluene (200 mL) to the Sub 1-I-1 synthesis To obtain 6.9 g of the product. (Yield: 81%).

(2) Sub 1-5 synthesis

2,3-dibromonaphthalene (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.0 g, 50 mmol) were added to Sub 1-I-5 (6.9 g, , THF (180 mL) and water (90 mL) were obtained 7.2 g of the product using the Sub 1-1 synthesis method. (Yield: 75%).

1.3. Sub 1-7 Synthetic Example

(1) Sub 1-I-7 synthesis

Di ([1,1'-biphenyl] -3-yl) amine (7.8 g, 24 mmol) and Pd ₂ (dba) ₃ (0.7 g, 24 mmol) were added to the starting material (4-chlorophenyl) boronic acid 0.7mmol), P (t-bu ) 3 (0.3g, 1.5mmol), NaO t -Bu (7.0g, 73mmol), toluene (250 mL) to the product using the Sub 1-I-1 9.0 synthesis g. (Yield: 84%)

(2) Sub 1-7 Synthesis

2,3-dibromonaphthalene (7.0 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.5 g, 61 mmol) were added to Sub 1-I-7 (9.0 g, 20 mmol) , THF (220 mL) and water (110 mL) were obtained using the above Sub 1-1 synthesis method. (Yield: 67%).

1.4. Sub 1-8 Synthetic Example

(1) Sub 1-I-8 synthesis

9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (6.0 g, 21 mmol) and Pd ₂ (dba) ₃ (0.6 g, 21 mmol) were added to the starting material (4-chlorophenyl) boronic acid (0.6 g, 0.6 mmol), P (t-bu) ₃ (0.3 g, 1.3 mmol), NaO t- Bu (6.1 g, 63 mmol) and toluene 7.4 g. (Yield: 87%).

(2) Sub 1-8 synthesis

2,3-dibromonaphthalene (6.3 g, 22 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.2 g, 55 mmol) were added to Sub 1-I-8 (7.4 g, 18 mmol) , THF (200 mL) and water (100 mL) were obtained 7.0 g of the product using the Sub 1-1 synthesis method. (Yield: 68%).

1.5. Sub 1-10 Synthetic Example

(1) Sub 1-I-10 synthesis

4-yl) dibenzo [b, d] thiophen-4-amine (8.1 g, 23 mmol) was added to a starting material (4-chlorophenyl) boronic acid (3.6 g, 23 mmol) _{, Pd 2 (dba) 3 (} 0.6g, 0.7mmol), P (t-bu) 3 (0.3g, 1.4mmol), NaO t -Bu (6.6g, 69mmol), toluene (230 mL) to the Sub 1 -I-1 < / RTI > synthetic method was used to obtain 9.1 g of the product. (Yield: 84%)

(2) Sub 1-10 Synthesis

2,3-dibromonaphthalene (6.6 g, 23 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.3 g, 58 mmol) were added to Sub 1-I-10 (9.1 g, 19 mmol) , THF (200 mL) and water (100 mL) were obtained by using the above Sub 1-1 synthesis method. (Yield: 62%).

1.6 Sub 1-11 Synthetic Example

(1) Sub 1-I-11 synthesis

(Naphthalen-1-yl) dibenzo [b, d] furan-4-amine (8.5 g, 28 mmol), Pd ₂ (dba) ₃ (0.8g, 0.8mmol), P ( t-bu) 3 (0.3g, 1.6mmol), NaO t -Bu (8.0g, 83mmol), toluene (275 mL) using the Sub 1-I-1 synthesis To obtain 9.4 g of a product. (Yield: 80%).

(2) Sub 1-11 synthesis

2,3-dibromonaphthalene (7.5 g, 26 mmol), Pd (PPh ₃ ) ₄ (0.8 g, 0.7 mmol) and NaOH (2.6 g, 66 mmol) were added to Sub 1-I-11 (9.4 g, , THF (240 mL) and water (120 mL) were obtained using the Sub 1-1 synthesis method described above to obtain 9.3 g of the product. (Yield: 72%).

1.7. Sub 1-13 Synthetic Example

(1) Sub 1-I-13 synthesis

To the starting material, (4-chlorophenyl) boronic acid (2.9 g, 19 mmol) was added N - ([1,1'-biphenyl] -3-yl) -9,9'- spirobi [fluoren] _{, 19mmol), Pd 2 (dba} ) 3 (0.5g, 0.68mmol), P (t-bu) 3 (0.2g, 1.1mmol), NaO t -Bu (5.4g, 56mmol), toluene (180 mL) to 9.5 g of the product was obtained using the Sub 1-I-1 synthesis method. (Yield: 85%).

(2) Sub 1-13 synthesis

2,3-dibromonaphthalene (5.4 g, 19 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (1.9 g, 47 mmol) were added to Sub 1-I-13 (9.5 g, , THF (170 mL) and water (85 mL) were obtained by using the above Sub 1-1 synthesis method. (Yield: 67%).

1.8. Sub 1-15 Synthetic Example

(1) Sub 1-I-15 synthesis

To the starting material, (4-chlorophenyl) boronic acid (3.0 g, 19 mmol) was added N - ([1,1'-biphenyl] -3-yl) -9,9'-spirobi [fluoren] _{, 19mmol), Pd 2 (dba} ) 3 (0.5g, 0.6mmol), P (t-bu) 3 (0.2g, 1.2mmol), NaO t -Bu (5.5g, 58mmol), toluene (190 mL) to 9.8 g of the product was obtained using the Sub 1-I-1 synthesis method. (Yield: 88%).

(2) Sub 1-15 Synthesis

2,3-dibromonaphthalene (5.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.0 g, 51 mmol) were added to Sub 1-I-15 (9.8 g, , THF (180 mL), and water (90 mL) were obtained by using the above Sub 1-1 synthesis method. (Yield: 75%).

1.9. Sub 1-18 Synthetic Example

(1) Sub 1-I-18 synthesis

To the starting material (4-chlorophenyl) boronic acid (4.2 g, 27 mmol) was added N - ([1,1'-biphenyl] -3-yl) -9,9'- spirobi [fluoren] _{, 27mmol), Pd 2 (dba} ) 3 (0.7g, 0.8mmol), P (t-bu) 3 (0.3g, 1.6mmol), NaO t -Bu (7.7g, 81mmol), toluene (270 mL) to Using the Sub 1-I-1 synthesis method, 10.8 g of the product was obtained. (Yield: 86%)

(2) Sub 1-18 Synthesis

2,3-dibromonaphthalene (8.0 g, 28 mmol), Pd (PPh ₃ ) ₄ (0.8 g, 0.7 mmol) and NaOH (2.8 g, 70 mmol) were added to Sub 1-I-18 (10.8 g, 23 mmol) , THF (250 mL), and water (125 mL) were obtained using the Sub 1-1 synthesis method described above to obtain 9.3 g of the product. (Yield: 64%).

1.10. Sub 1-20 Synthetic Example

(1) Sub 1-I-20 synthesis

2-amine (6.9 g, 26 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol) and P (t-Bu) were added to the starting material (4-chlorophenyl) boronic acid ) ₈ (0.3 g, 1.5 mmol), NaO t- Bu (7.4 g, 77 mmol) and toluene (250 mL). (Yield: 81%).

(2) Sub 1-20 synthesis

2,3-dibromonaphthalene (7.1 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.5 g, 62 mmol) were added to Sub 1-I-20 (8.0 g, 21 mmol) , THF (220 mL) and water (110 mL) were obtained 6.8 g of the product using the Sub 1-1 synthesis method. (Yield: 60%).

1.11. Sub 1-24 Synthetic Example

(1) Sub 1-I-24 synthesis

([1,1'-biphenyl] -4-yl-2 ', 3', 4 ', 5', 6'-d5) was added to the starting material (3-chlorophenyl) boronic acid dibenzo [b, d] furan- 3-amine (7.4g, 22mmol), Pd 2 (dba) 3 (0.6g, 0.7mmol), P (t-bu) 3 (0.3g, 1.3mmol), NaO t - Bu (6.3 g, 65 mmol) and toluene (210 mL) were obtained using the above Sub 1-I-1 synthesis method. (Yield: 81%).

(2) Sub 1-24 synthesis

2,3-dibromonaphthalene (6.0 g, 21 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.1 g, 53 mmol) were added to Sub 1-I-24 (8.1 g, 18 mmol) , THF (200 mL) and water (100 mL) were obtained 7.3 g of the product using the Sub 1-1 synthesis method. (Yield: 67%).

1.12. Sub 1-25 Synthetic Example

(1) Sub 1-I-25 synthesis

2-yl) dibenzo [b, d] furan-2-amine (8.3 g, 26 mmol) and Pd ₂ (2 mmol) were added to the starting material (3-chlorophenyl) boronic acid _{(dba) 3 (0.7g, 0.8mmol} ), P (t-bu) 3 (0.3g, 1.5mmol), NaO t -Bu (7.4g, 77mmol), toluene (250 mL) of the Sub-1 I- 1 synthetic method was used to obtain 9.0 g of the product. (Yield: 79%).

(2) Sub 1-25 Synthesis

2,3-dibromonaphthalene (7.0 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 61 mmol) were added to Sub 1-I- , THF (220 mL) and water (110 mL) were obtained using the above Sub 1-1 synthesis method. (Yield: 64%).

1.13. Sub 1-26 Synthetic Example

(1) Sub 1-I-26 synthesis

9-dimethyl-N- (3- (naphthalen-2-yl) phenyl) -9H-fluoren-2-amine (6.3 g, 15 mmol) was added to the starting material (3-chlorophenyl) boronic acid ), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol), P (t-bu) ₃ (0.2 g, 0.9 mmol), NaO t- 1-I-1 synthesis method was used to obtain 7.0 g of the product. (Yield: 86%)

(2) Sub 1-26 Synthesis

2,3-dibromonaphthalene (4.5 g, 16 mmol), Pd (PPh ₃ ) ₄ (0.5 g, 0.4 mmol) and NaOH (1.6 g, 40 mmol) were added to Sub 1-I- , THF (140 mL) and water (70 mL) were obtained 6.2 g of the product using Sub 1-1 synthesis method. (Yield: 68%).

1.14. Sub 1-30 Synthetic Example

(1) Sub 1-I-30 synthesis

(9.3-dimethyl-9H-fluoren-2-yl) -N-phenylaniline (8.3 g, 23 mmol) and Pd ₂ (dba) were added to the starting material (3-chlorophenyl) boronic acid _{3 (0.6g, 0.7mmol), P} (t-bu) 3 (0.3g, 1.4mmol), NaO t -Bu (6.6g, 69mmol), toluene (230 mL) to the Sub 1-I-1 synthesis To obtain 9.4 g of the product. (Yield: 77%)

(2) Sub 1-30 synthesis

2,3-dibromonaphthalene (6.1 g, 21 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.1 g, 53 mmol) were added to Sub 1-I-30 (9.4 g, 18 mmol) , THF (190 mL) and water (95 mL) were obtained using the above Sub 1-1 synthesis method. (Yield: 66%).

1.15. Sub 1-32 Synthetic Example

(1) Sub 1-I-32 synthesis

Yl) phenyl) - [1,1'-biphenyl] -3-amine (7.6 g, 21 mmol) was added to the starting material (3-chlorophenyl) boronic acid (3.2 g, 21 mmol) _{, Pd 2 (dba) 3 (} 0.6g, 0.6mmol), P (t-bu) 3 (0.3g, 1.2mmol), NaO t -Bu (6.0g, 61mmol), toluene (200 mL) to the Sub 1 -I-1 < / RTI > synthesis was used to obtain 8.6 g of the product. (Yield: 79%).

(2) Sub 1-32 Synthesis

2,3-dibromonaphthalene (5.6 g, 19 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (1.9 g, 49 mmol) were added to Sub 1-I-32 (8.6 g, 16 mmol) , THF (180 mL) and water (90 mL) were obtained by using the above Sub 1-1 synthesis method. (Yield: 71%).

1.16. Sub 1-33 Synthetic Example

(1) Sub 1-I-33 synthesis

[(1,1'-biphenyl) -4-yl) dibenzo [b, d] furan-3-amine (7.5 g, 22 mmol) was added to the starting material (2-chlorophenyl) boronic acid _{, Pd 2 (dba) 3 (} 0.6g, 0.7mmol), P (t-bu) 3 (0.3g, 1.3mmol), NaO t -Bu (6.5g, 67mmol), toluene (220 mL) to the Sub 1 -I-1 < / RTI > synthesis method was used to obtain 8.9 g of the product. (Yield: 75%).

(2) Sub 1-33 Synthesis

2,3-dibromonaphthalene (5.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) and NaOH (2.0 g, 50 mmol) were added to Sub 1-I-33 (8.9 g, , THF (180 mL) and water (90 mL) were obtained by using the above Sub 1-1 synthesis method. (Yield: 71%).

On the other hand, the compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 1 shows the FD-MS value of the compound belonging to Sub 1.

[Table 1]

II. Synthesis of Sub 2

Sub 2 can be synthesized by the following reaction scheme, but is not limited thereto.

2.1. Sub 2-1 Synthetic Example

To a round bottom flask (4-chlorophenyl) boronic acid ( 5.0g, 32mmol), diphenylamine (5.4g, 32mmol), Pd 2 (dba) 3 (0.9g, 1mmol), P (t-bu) 3 (0.4g, , NaO t- Bu (9.2 g, 95 mmol) and toluene (320 mL) were added thereto, and the reaction was allowed to proceed at 100 ° C. 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 subjected to silicagel column and recrystallization to obtain 8.0 g of Sub 2-1. (Yield: 87%).

2.2 Sub 2-2 Synthetic Example

(6.7 g, 31 mmol), Pd ₂ (dba) ₃ (0.8 g, 1 mmol) and P (t-bu) were added to the starting material (4-chlorophenyl) boronic acid ₃ (0.4g, 2mmol), NaO t- Bu (8.9g, 92mmol) and toluene (300mL). Sub 2-1 synthesis was used to obtain 8.3g of the product. (Yield: 80%).

2.3. Sub 2-4 Synthetic Example

To the starting material (4-chlorophenyl) boronic acid (3.0 g, 19 mmol) was added N - ([1,1'-biphenyl] -4-yl) -9,9'- spirobi [fluoren] _{, 19mmol), Pd 2 (dba} ) 3 (0.5g, 1mmol), P (t-bu) 3 a (0.2g, 1mmol), NaO t -Bu (5.5g, 58mol), toluene (200 mL) the Sub Using the 2-1 synthetic method, 8.5 g of the product was obtained. (Yield: 73%)

2.4. Sub 2-5 Synthetic Example

[(1,1'-biphenyl) -4-yl) dibenzo [b, d] thiophen-2-amine (7.9 g, 22 mmol) was added to a starting material, (3-chlorophenyl) boronic acid _{, Pd 2 (dba) 3 (} 0.6g, 0.7mmol), P (t-bu) 3 (0.3g, 1mmol), NaO t -Bu (6.5g, 67mol), toluene (220 mL) to the Sub 2- 1 < / RTI > synthesis was used to obtain 8.2 g of the product. (Yield: 78%).

2.5. Sub 2-7 Synthetic Example

(Naphthalen-2-yl) naphthalen-1-amine (7.2 g, ₂₇ mmol) and Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol) were added to the starting material (2-chlorophenyl) boronic acid ), P (t-bu) ₃ (0.3 g, 1.6 mmol), NaO t- Bu (7.7 g, 80 mol) and toluene (270 mL). (Yield: 79%).

2.6. Sub 2-10 Synthetic Example

Dibenzo [b, d] furan-4-amine (7.1 g, 23 mmol) and Pd ₂ (dba) ₃ ( ₃ g) were added to a starting material (3-chlorophenyl) boronic acid (0.6 g, 0.7 mmol), P (t-bu) ₃ (0.3 g, 1.4 mmol), NaO t- Bu (6.6 g, 69 mol) and toluene (230 mL) . (Yield: 81%).

2.7. Sub 2-12 synthesis example

(9,9-dimethyl-9H-fluoren-2-yl) -9,9-diphenyl-9H-fluoren-2-amine (8.7 g, 17 mmol) was added to the starting material (4-chlorophenyl) _{g, 17mmol), Pd 2 (} dba) 3 (0.5g, 0.5mmol), P (t-bu) 3 (0.2g, 1mmol), NaO t -Bu (4.8g, 50mol), toluene (170 mL) to 8.1 g of the product was obtained using the above Sub 2-1 synthesis method. (Yield: 75%).

2.8. Sub 2-13 Synthetic Example

(Naphthalen-1-yl) -9,9-diphenyl-9H-fluoren-2-amine (8.2 g, 18 mmol) and Pd ₂ (4 mmol) were added to a starting material (4-chlorophenyl) boronic acid _{dba) 3 (0.5g, 0.5mmol)} , P (t-bu) 3 (0.2g, 1mmol), NaO t -Bu (5.2g, 54mol), toluene (180 mL) using the Sub 2-1 synthesis To obtain 8.0 g of a product. (Yield: 77%)

2.9. Sub 2-15 Synthetic Example

(7.5 g, 22 mmol) and Pd ₂ (dba) were added to the starting material (3-chlorophenyl) boronic acid (3.4 g, 22 mmol) ₃ (0.6 g, 0.6 mmol), P (t-bu) ₃ (0.3 g, 1.3 mmol), NaO t- Bu (6.3 g, 65 mol) and toluene (210 mL) 8.2 g of the product was obtained. (Yield: 81%).

2.10. Sub 2-16 Synthetic Example

(8.0 g, 23 mmol), Pd ₂ (dba) ₃ ((2-chlorophenyl) boronic acid (3.6 g, 23 mmol) (0.6 g, 0.7 mmol), P (t-bu) ₃ (0.3 g, 1.4 mmol), NaO t- Bu (6.6 g, 69 mol) and toluene (230 mL) 8.1 g. (Yield: 76%).

On the other hand, the compound belonging to Sub 2 may be, but not limited to, the following compound, and Table 2 shows the FD-MS value of the compound belonging to Sub 2.

[Table 2]

III. Product synthesis

Sub 1 (1 eq.) Was dissolved in THF in a round bottom flask and Sub 2 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.) And H ₂ O were added and heated at 80 ° C Lt; / RTI > After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain final product.

1. Example of P-2 synthesis

Sub 1-38 (6.0 g, 13.4 mmol) obtained in the above synthesis was dissolved in THF (140 mL) in a round bottom flask and Sub 2-3 (5.9 g, 13.4 mmol) and Pd (PPh ₃ ) ₄ , 0.40 mmol), NaOH (1.6 g, 40.1 mmol) and water (70 mL) were added and stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 7.2 g (yield: 70%) of the product.

2. Example of P-3 synthesis

Sub 2-17 (6.97 g, 14.8 mmol) and Pd (PPh ₃ ) ₄ (0.51 g, 0.40 mmol) were dissolved in THF (140 mL) , NaOH (1.77 g, 44.4 mmol) and water (70 mL) were obtained 8.9 g (Yield: 71%) of the product using the above P-2 synthesis method.

3. Example of P-8 synthesis

Sub 2-18 (5.83 g, 15.4 mmol) and Pd (PPh ₃ ) ₄ (0.53 g, 0.50 mmol) were dissolved in THF (150 mL) , NaOH (1.85 g, 46.2 mmol) and water (75 mL) were used to obtain 9.1 g (yield: 76%) of the product using the above P-2 synthesis method.

4. Example of P-14 synthesis

Sub 2-2 (3.9 g, 11.6 mmol) and Pd (PPh ₃ ) ₄ (0.4 g, 0.30 mmol) were dissolved in THF (110 mL) , NaOH (1.39 g, 34.7 mmol) and water (55 mL) were used to obtain 7.8 g (yield: 75%) of the product using the above P-3 synthesis method.

5. Example of P-40 synthesis

Sub 2-3 (2.34 g, 5.3 mmol) and Pd (PPh ₃ ) ₄ (0.2 g, 0.20 mmol) were dissolved in THF (50 mL) to Sub 1-8 (3 g, 5.3 mmol) , NaOH (0.64 g, 15.9 mmol) and water (25 mL) were used to obtain 3.2 g (yield: 68%) of the product using the above P-3 synthesis method.

6. P-54 Synthetic Example

After the Sub 1-56 (5.8 g, 10.1 mmol ) obtained in the above Synthesis was dissolved in THF (100 mL), Sub 2-43 (4.18 g, 10.1 mmol), Pd (PPh 3) 4 (0.35 g, 0.30 mmol) , NaOH (1.21 g, 30.2 mmol) and water (50 mL) were obtained 5.6 g (Yield: 64%) of the product using the above P-2 synthesis method.

7. Example of P-61 synthesis

Sub-2-49 (6.85 g, 13.0 mmol) and Pd (PPh ₃ ) ₄ (0.45 g, 0.40 mmol) were dissolved in THF (130 mL) , NaOH (1.56 g, 39.0 mmol) and water (65 mL) were obtained 8.7 g (Yield: 74%) of the product using the above P-2 synthesis method.

8. Example of P-68 synthesis

(3.3 g, 9.0 mmol) and Pd (PPh ₃ ) ₄ (0.31 g, 0.30 mmol) were dissolved in THF (90 mL) to Sub 1-66 (5.0 g, 9.0 mmol) , NaOH (1.08 g, 27.0 mmol) and water (45 mL) were obtained by using the above P-2 synthesis method to obtain 5.6 g (yield: 77%) of the product.

9. Example of P-70 synthesis

After the Sub 1-68 (6.2 g, 10.8 mmol ) obtained in the above Synthesis was dissolved in THF (110 mL), Sub 2-57 (4.8 g, 10.8 mmol), Pd (PPh 3) 4 (0.37 g, 0.30 mmol) , NaOH (1.29 g, 32.3 mmol) and water (55 mL) were obtained 6.6 g (Yield: 68%) of the product using the above P-2 synthesis method.

10. P-81 Synthetic Example

Sub 2-19 (2.34 g, 5.3 mmol) and Pd (PPh ₃ ) ₄ (0.2 g, 0.20 mmol) were dissolved in THF (50 mL) to Sub 1-8 (3 g, 5.3 mmol) , NaOH (0.64 g, 15.9 mmol) and water (25 mL) were used to obtain 3.3 g (yield: 70%) of the product using the above P-3 synthesis method.

11. Example of P-89 synthesis

10 (4.6 g, 10.7 mmol) and Pd (PPh ₃ ) ₄ (0.37 g, 0.30 mmol) were dissolved in THF (100 mL) to Sub 1-16 (7.2 g, 10.7 mmol) , NaOH (1.28 g, 32.1 mmol) and water (50 mL) were obtained 6.8 g (Yield: 65%) of the product using the above P-3 synthesis method.

12. P-91 Synthetic Example

Sub 2-74 (2.5 g, 6.5 mmol) and Pd (PPh ₃ ) ₄ (0.23 g, 0.20 mmol) were dissolved in THF (66 mL) , NaOH (0.78 g, 19.6 mmol) and water (33 mL) were used to obtain 4.6 g (yield: 74%) of the product using the above P-2 synthesis method.

13. P-92 Synthetic Example

After the Sub 1-3 (6.8 g, 13.0 mmol ) obtained in the above Synthesis was dissolved in THF (130 mL), Sub 2-33 (4.7 g, 13.0 mmol), Pd (PPh 3) 4 (0.45 g, 0.40 mmol) , NaOH (1.55 g, 38.7 mmol) and water (65 mL) were used to obtain 7.5 g (Yield: 76%) of the product using the above P-2 synthesis method.

Meanwhile, the FD-MS values of the compounds P-1 to P-92 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Evaluation of manufacturing of organic electric device

[Example 1] Green 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 deposited on the ITO layer (anode) To form a hole injection layer. Then, the compound P-1 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, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) 2") was added to the hole transport layer as a host material using 4,4'-N, N'-dicarbazole- ) ₃ ") was used as a dopant material and doped in a ratio of 90:10 by weight to form a light emitting layer by vacuum evaporation to a thickness of 30 nm. 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.

[Examples 2 to 42] A green organic electroluminescent device (hole transport layer)

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compounds P-2 to P-92 of the present invention described in Table 5 were used instead of the compound P-1 of the present invention as the hole transport layer material.

[Comparative Example 1] to [Comparative Example 6]

In Comparative Examples 1 to 6, organic electroluminescent devices were manufactured in the same manner as in Example 1, except that the following compounds 1 to 6 were used instead of the compound P-1 of the present invention as the hole transport layer material Respectively.

Electroluminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 42 and Comparative Examples 1 to 6 , And the T95 lifetime was measured through a life measuring device manufactured by Mac Science Inc. at a reference luminance of 5000 cd / m ² . Table 4 below shows the results of evaluation of the device characteristics for Examples 1 to 42 and Comparative Examples 1 to 6.

[Table 4]

The device measurement results in Table 4 show that the organic electroluminescent devices using the compounds P-1 to P-92 of the present invention as the hole transport layer materials are lower in the organic electroluminescent devices using Comparative Compounds 1 to 6 as the hole transport layer materials It can be confirmed that not only the driving voltage and the luminous efficiency but also the lifetime are remarkably improved.

Comparing Compounds 2 to 5 are structurally similar. Comparing Compounds 2 to 4 have a phenyl group as a connecting group in the naphthalene core as a center, And Comparative Example 5 has the same central core as Comparative Compound 4 but has a structure in which an amine group (-N (Ar ¹ ) (Ar ² )) is bonded instead of a carbazole. to be.

In Table 4, which is an embodiment of the organic light-emitting device used as the hole transporting layer, it was confirmed that the comparison compound 2 in which all of the central naphthalene was substituted with hydrogen was more efficient and longer in life than the Comparative Compound 3 in which one phenyl was substituted , And Comparative Example 4 in which phenyl is substituted with 2, efficiency and life are reduced as compared with Comparative Compound 3 in which one phenyl is substituted. This is because the substitution of the phenyl group for the naphthalene, which is the center core, reduces the packing density during the fabrication of the device, thereby lowering the hole mobility.

On the other hand, when comparing the comparative compound 4 and the comparative compound 5, the comparative compound 5 differs from the comparative compound 4 in that the carbazolyl group of the comparative compound 4 is replaced with an arylamine. When these compounds are used as a hole transport layer material, It is understood that the device characteristics of the second embodiment are excellent. Therefore, it can be seen that, in the case of having a similar macronucleus skeleton, it is advantageous in terms of the efficiency and lifetime of the device that the amine group is bonded rather than the carbazole is bonded to phenylene of the mother nucleus.

Similarly, when comparing the compound of the present invention with the compound of Comparative Example 2, which is the most efficient and the most excellent of the lifetime among Comparative Examples, the compound of Comparative Example 2 in which the substituent bonded to phenylene of the mother nucleus is a carbazolyl group, Are amine groups. From the characteristics of the devices using these compounds, it can be confirmed that the compound of the present invention is improved in terms of lifetime and efficiency.

Therefore, when the compound of the present invention in which all of the central naphthalene is substituted with hydrogen and the amine group is bonded to phenylene of the mother nucleus is used as a hole transporting layer material, the efficiency and lifetime of the device can be further improved. Mobility, and packing density.

[Example 43] A green organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer, and N, N'-bis (1-naphthalenyl) -N N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as "NPB") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the compound P-1 of the present invention on the hole transport layer and then forming a vacuum-deposited to the light-emitting auxiliary layer with a thickness of 20 nm, CBP on the light emitting auxiliary layer as a host material, dopant, the Ir (ppy) ₃ And doped in a weight ratio of 90:10, followed by vacuum evaporation to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer 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.

[Examples 44 to 84] A green organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated in the same manner as in Example 43 except that the compounds P-2 to P-92 of the present invention described in Table 5 were used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material .

[Comparative Example 7] to [Comparative Example 12]

In Comparative Example 7, an organic electroluminescent device was fabricated in the same manner as in Example 43 except that the luminescent auxiliary layer was not formed. In Comparative Examples 8 to 12, the compound of the present invention P-1 was replaced with the above-mentioned Comparative Compound 6, an organic electroluminescent device was fabricated in the same manner as in Example 43.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 43 to 84 and Comparative Examples 7 to 12 of the present invention And the T95 lifetime was measured through a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 5000 cd / m ^2. The measurement results are shown in Table 5 below.

[Table 5]

[Example 85] A red organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer. Then, NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer Respectively. Subsequently, Compound P-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer. Then, CBP (bis- (1-phenylisoquinolyl) Iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") as a dopant was doped at a weight ratio of 95: 5 and vacuum deposited to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer 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.

[Examples 86 to 126] Red organic electroluminescence device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated in the same manner as in Example 85 except that the compounds P-2 to P-92 of the present invention described in Table 6 below were used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material .

[Comparative Example 12] to [Comparative Example 17]

In Comparative Example 12, an organic electroluminescent device was fabricated in the same manner as in Example 85 except that no luminescent auxiliary layer was formed. In Comparative Examples 13 to 17, the compound of the present invention An organic electroluminescent device was fabricated in the same manner as in Example 85 except that the above Comparative Compounds 2 to 6 were used in place of P-1.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 85 to 126 and Comparative Examples 12 to 17 of the present invention And the T95 lifetime was measured by a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 2500 cd / m ^2. The measurement results are shown in Table 6 below.

[Table 6]

[Example 127] A blue organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer. Then, NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer Respectively. Subsequently, Compound P-1 of the present invention was vacuum deposited on the hole transport layer to a thickness of 20 nm to form an emission assist layer, and 9,10-Di (2-naphthyl) anthracene (Hereinafter abbreviated as " ADN ") was used as a host material and BD-052X (manufactured by Idemitsu Kosan) was used as a dopant in a ratio of 93: 7 by weight to form a light emitting layer by vacuum deposition to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq3 was vacuum deposited to a thickness of 40 nm on the hole blocking layer 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.

[Examples 128 to 169] A blue organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated in the same manner as in Example 127 except that the compounds P-2 to P-92 of the present invention described in Table 7 were used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material .

[Comparative Example 18] to [Comparative Example 23]

In Comparative Example 18, an organic electroluminescent device was fabricated in the same manner as in Example 127 except that no luminescent auxiliary layer was formed. In Comparative Examples 19 to 23, the compound of the present invention An organic electroluminescent device was fabricated in the same manner as in Example 85 except that the above Comparative Compounds 2 to 6 were used in place of P-1.

The organic EL devices manufactured in Examples 126 to 169 and Comparative Examples 18 to 23 according to the present invention were prepared by applying a forward bias DC voltage to the electroluminescence (EL) characteristic by photoresearch PR-650 And the T95 lifetime was measured by a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 500 cd / m ^2. The measurement results are shown in Table 7 below.

[Table 7]

From Table 7, it can be seen that the organic electroluminescent device using the compound of the present invention for the light-emission-facilitating layer significantly improves the luminous efficiency and life span. It was confirmed that the efficiency and lifetime were increased in the presence of the luminescent auxiliary layer as compared with the case where the luminescent auxiliary layer was not present and it was confirmed that the efficiency and lifetime were further increased when the luminescent auxiliary layer was formed from the compound of the present invention I could. Particularly, among the compounds of the present invention, the case where the substituent (Ar ¹ or Ar ² ) substituted in the amine (-N (Ar ¹ ) (Ar ² )) is an aryl group is more preferable than the compound having a heterocyclic ring as a substituent, And the results are shown in Fig.

The reason why the efficiency of the compound of the present invention is improved when the compound of the present invention is used as the luminescent auxiliary layer is that the HOMO energy level of the compound of the present invention does not greatly differ from that of the hole transport layer (HTL) The charge balance in the light emitting layer is adjusted so that the generation of excess polaron is reduced and thereby the dopant quenching is reduced. As a result, Is expected to improve. In addition, since the compound of the present invention has a high T ₁ , electrons reversely migrating from the light emitting layer to the hole transporting layer are blocked, thereby reducing thermal damage due to light emission in the hole transporting layer, thereby increasing efficiency and lifetime.

In the evaluation results of the device fabrication described above, the device characteristics of applying the compound of the present invention to only one of the hole transporting layer and the light emitting auxiliary layer have been described. However, the compound of the present invention may be used by applying both the hole transporting layer and the light emitting auxiliary 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 claims, and all the 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 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

Claims (10)

A compound represented by the following formula (1):
≪ Formula 1 >

In Formula 1,
Ar ¹ to Ar ⁴ independently represent C ₆ -C ₆₀ An aryl group; A fluorenyl group; O, N, S, Si, and P, and at least one heteroatom selected from the group consisting of C ₂ -C ₆₀ A heterocyclic group; C ₁ -C ₆₀ An alkyl group; And C ₆ -C ₆₀ Aromatic rings and C ₃ -C ₆₀ A fused ring group of an aliphatic ring,
R ¹ and R ² independently of one another are deuterium; Tritium; A halogen group; Cyano; A nitro group; C ₆ -C ₆₀ An aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} ~ 60 containing at least one hetero atom of Si and P; C ₆ -C ₆₀ Aromatic rings and C ₃ -C ₆₀ A fused ring group of an aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group. When a plurality of neighboring R ¹ and R ² groups are present, adjacent R ¹ groups or adjacent R ² groups may be bonded to each other to form a ring. M and n are each an integer of 0 to 4,
Wherein Ar ¹ to Ar ⁴ is an aryl group, a fluorenyl group, when heteroaryl is a ring group, a fusion ring group, or an alkyl group and R ¹ and R ² is an aryl group, a fluorenyl group, a heterocyclic group, a fusion ring group, an alkyl group, An alkenyl group, an alkynyl group, an alkynyl group, an alkoxy group, or an aryloxy group, each of these may be substituted with deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And -LN (R ') (R "); wherein L in LN (R') (R") is a single bond; An arylene group; A fluorenylene group; A divalent heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one hetero atom of Si and P; And a divalent fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; and R 'and R "are independently selected from the group consisting of a C ₆ -C ₆₀ aryl group, A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, a C ₁ -C ₆₀ alkyl group, and a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic A fused ring group of a ring; The method according to claim 1,
(1) is represented by one of the following Chemical Formulas (2) to (7):

In the general formulas (2) to (7), Ar ¹ to Ar ⁴ , R ¹ , and R ² are the same as defined in claim 1. The method of claim 1, wherein
Wherein the compound of formula (I) is one of the following compounds:

. A first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode,
Wherein the organic material layer comprises a compound according to any one of claims 1 to 3. 5. The method of claim 4,
Wherein the compound is contained in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer and the light emitting layer of the organic material layer, and the compound is a single kind of compound or a mixture of two or more kinds. 6. The method of claim 5,
Wherein the compound is included in the light-emission-assisting layer. 5. The method of claim 4,
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. 5. The method of claim 4,
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. A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device. 10. The method of claim 9,
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.