WO2015111888A1

WO2015111888A1 - Compound for organic electric element, organic electric element using same, and electronic device thereof

Info

Publication number: WO2015111888A1
Application number: PCT/KR2015/000551
Authority: WO
Inventors: 이범성; 문성윤; 김대성; 박정철; 이규민; 이선희
Original assignee: 덕산네오룩스 주식회사
Priority date: 2014-01-22
Filing date: 2015-01-20
Publication date: 2015-07-30

Abstract

Disclosed is a compound represented by formula 1. Further disclosed is an organic electric element comprising: a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises the compound represented by formula 1. When the organic layer comprises the compound represented by formula 1, the organic electric element may have enhanced light-emitting efficiency, stability, and life span.

Description

Compound for organic electric element, organic electric element using same and electronic device thereof

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

Currently, the portable display market is increasing in size with large-area displays, which requires more power consumption than that required in conventional portable displays. Therefore, power consumption has become an important factor for a portable display having a limited power source such as a battery, and efficiency and life problems are also important factors to be solved.

Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage decreases relatively, and the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. The lifespan tends to increase. However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level, T1 value, and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emitting auxiliary according to each light emitting layer (R, G, B). It is time to develop the floor.

In general, 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 generate excitons by recombination.

However, in the case of the material used in the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes the exciton generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This results in light emission in the hole transport layer or at the interface of the hole transport layer, resulting in reduced color purity, reduced efficiency, and low life.

In addition, when a material having a high hole mobility is used to make a low driving voltage, the efficiency tends to decrease. Since hole mobility is faster than electron mobility in a general organic electroluminescent device, it causes charge unbalance in the light emitting layer, resulting in reduced efficiency and low lifespan.

Therefore, the light emitting auxiliary layer has a hole mobility (in the range of the blue device driving voltage of a full device) and a high T1 (electron block) value to have a suitable driving voltage to solve the problems of the hole transport layer. It must be a material with a wide bandgap, but this cannot simply be a structural characteristic of the core of the luminescent auxiliary layer material, but a combination of the core and sub-substituent properties of the material. When possible. Therefore, in order to improve the efficiency and lifespan of the organic electric device, development of a light emitting auxiliary layer material having a high T1 value and a wide band gap is urgently required.

That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc., are stable and efficient. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light emitting auxiliary layer and the hole transport layer is urgently required.

An object of the present invention is to provide a compound capable of improving the luminous efficiency, stability and lifetime of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the following formula.

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

By using a non-linear coupler in the carbazole core, by using the compound according to the present invention having a wide bandgap and a high T1 value, high luminous efficiency and high heat resistance of the device can be achieved. The color purity and lifespan of the device can be improved.

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

[Description of the code]

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

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected". In addition, if a component such as a layer, film, region, plate, etc. is said to be "on" or "on" another component, it is not only when the other component is "on top of" but also another component in between. It is to be understood that this may also include cases. On the contrary, when a component is said to be "directly above" another part, it should be understood to mean that there is no other part in the middle.

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows.

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

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.

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

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R 'and R "are all hydrogen in the following structures, unless otherwise stated, and" 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' are bonded to each other to form a carbon It includes the case of forming a compound by spying together.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. The aryl group or arylene group in the present invention includes monocyclic, ring conjugate, conjugated ring system, spiro compound and the like.

As used herein, the term "heterocyclic group" includes not only aromatic rings, such as "heteroaryl groups" or "heteroarylene groups," but also non-aromatic rings, and unless otherwise specified, each carbon number includes one or more heteroatoms. It means a ring of 2 to 60, but is not limited thereto. As used herein, the term “heteroatom” refers to N, O, S, P or Si unless otherwise indicated, and heterocyclic groups are monocyclic, ring conjugates, conjugated multiple ring systems, spies, including heteroatoms. Means a compound or the like.

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

As used herein, the term “ring” includes monocyclic and polycyclic rings, includes hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and nonaromatic rings.

As used herein, the term "polycyclic" includes ring assemblies, fused multiple ring systems and spiro compounds, such as biphenyl, terphenyl, and the like, including aromatics as well as nonaromatics, hydrocarbons The ring as well includes heterocycles comprising at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (single or conjugated ring systems) are directly connected to each other through a single bond or a double bond and directly between such rings. It means that the number of linkages is one less than the total number of ring systems in this compound. Ring aggregates may have the same or different ring systems directly connected to each other via a single bond or a double bond.

As used herein, the term "conjugated multiple ring systems" refers to fused ring forms that share at least two atoms, including the ring systems of two or more hydrocarbons joined together and at least one heteroatom. And heterocyclic systems having at least one conjugated form. These conjugated several ring systems can be aromatic rings, heteroaromatic rings, aliphatic rings or combinations of these rings.

As used herein, the term "spiro compound" has a "spiro union", and a spiro linkage means a linkage formed by two rings sharing one atom only. In this case, the atoms shared by the two rings are called spiro atoms, and according to the number of spiro atoms in a compound, they are respectively referred to as 'monospyro-', 'diespyro-' and 'trispyro-' It is called a compound.

Also, when prefixes are named consecutively, it means that substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C ₁ -C ₂₀ alkyl groups, C ₁ -C ₂₀ alkoxyl group, C ₁ -C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl, 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 Substituted by at least one substituent selected from the group consisting of a group, a germanium group, 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 It is not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. In this case, 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, and the like. The electron transport layer 160 may serve as a hole blocking layer. You can do it.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.

Compound according to the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a light emitting layer 150, light efficiency improvement layer, light emitting auxiliary layer, etc. It can be used as a material. In one example, the compound of the present invention may be used as a material for the hole transport layer 140 and / or the light emitting auxiliary layer 151.

Meanwhile, even in the same core, the band gap, the electrical properties, and the interfacial properties may vary depending on which substituents are bonded at which positions, and therefore, the selection of the cores and the combination of sub substituents bonded thereto are very important. Long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the problem of light emission in the hole transport layer in the organic electroluminescent device, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and correspond to each light emitting layer (R, G, B). Therefore, it is necessary to form different emission auxiliary layers. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by forming a hole transport layer or a light emitting auxiliary layer using a compound represented by the formula (1) by optimizing the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) The lifetime and efficiency of the organic electric element can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a deposition method, for example, each layer may be formed using a deposition method such as PVD, CVD, or the like. In the organic electroluminescent device according to the present invention, for example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130 and the hole transport layer 140 thereon. ), And an organic material layer including the emission layer 150, the electron transport layer 160, and the electron injection layer 170, and then deposit a material that can be used as the cathode 180 thereon.

In addition, the organic layer may be formed using a variety of polymer materials, such as 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, a roll-to-roll process, a doctor blading process, It can be produced in fewer layers by a method such as a screen printing process or a thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which 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 therefrom. May also be applied to these WOLEDs.

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

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, 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 which concerns on one aspect of this invention is demonstrated.

Compound according to an aspect of the present invention is represented by the following formula (1).

In Formula 1, L is

or

to be. Here, the mark * indicates a position to be bonded to the nitrogen (N) of the amine group in the formula (1), a and b are each an integer of 0 to 4. In addition, R ³ and R ⁴ are independently of each other, i) deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; -L'-N (R ^a ) (R ^b ); And combinations thereof, or ii) at least one pair of neighboring groups, that is, adjacent R ³ , neighboring R ^4, and / or neighboring R ³ and R ^{4 in} combination with at least one; And R ³ and R ⁴ which do not form a ring are as defined in i). The ring formed by bonding of adjacent groups to each other may be monocyclic or polycyclic, and may be a C ₆ -C ₆₀ aromatic ring, a C ₂ -C ₆₀ hetero ring, a C ₃ -C ₆₀ alicyclic ring, or a combination thereof. Fused ring, etc., and may be a saturated or unsaturated ring.

When a is an integer of 2 or more, R ³ may be the same as or different from each other. When b is an integer of 2 or more, R ^{4 may} also be the same or different from each other.

Preferably, a and b are both hydrogen, or R ³ and R ⁴ may be an aryl group of C ₆ -C ₁₆ , a heterocyclic group of C ₅ -C ₉ , and preferably C ₆ , C ₁₀ , C Or an aryl group of ₁₂ or C ₁₆ , a heterocyclic group of C ₅ , C ₈ or C ₉ .

Also, preferably, R ³ and R ⁴ may be selected from the following structures independently of each other.

On the other hand, the ring formed by combining R ³ , R ^4, and / or neighboring groups with each other may include deuterium, halogen, silane, siloxane, boron, and germanium; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Of C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C _20. It may be further substituted with one or more substituents selected from the group consisting of.

In Chemical Formula 1, Ar ¹ to Ar ³ are each independently a C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C _{30 It} may be selected from the group consisting of or a combination thereof.

Preferably, Ar ¹ may be one of the following structures.

,

In the above structure, X is O, S or C (R ') (R "), wherein R' and R" are independently of each other, hydrogen; heavy hydrogen; Tritium; Aryl group of C ₆ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; And an alkenyl group of C ₂ -C ₂₀ ; and R ′ and R ″ may be bonded to each other to form a spiro compound together with the carbon to which they are bonded.

Preferably, Ar ¹ is

,

or

Where R ′ and R ″, o, p and the like are the same as defined above.

In the above structure, R ⁵ and R ⁶ are independently of each other, i) deuterium; Tritium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; And combinations thereof, or ii) adjacent groups may combine with each other to form at least one ring, provided that R ⁵ and R ⁶ which do not form a ring are as defined in i) above. same.

For example, when o and p are both 2, adjacent R ⁵ may be bonded to each other to form a ring, and R ⁶ may be an aryl group or a heterocyclic group independently from each other even if adjacent to each other. Of course, when o is an integer of 2 or more, a plurality of R ⁵ may be the same or different from each other, and some of the adjacent groups may be bonded to each other to form a ring, and the remaining groups that do not form a ring are selected from the substituent groups defined above Can be. The same is true when p is an integer of 2 or more.

Preferably, Ar ¹ is an aryl group of C ₆ -C ₂₅ , more preferably an aryl group of C ₆ -C ₁₈ , and preferably an aryl group such as C ₆ , C ₁₀ , C ₁₂ , C _18, etc. And they may be substituted with at least one deuterium. For example, Ar ¹ may be a phenyl group, a naphthyl group, a biphenylyl group, a terphenyl group, a phenyl group substituted with a biphenylyl group, and the like, which may be further substituted with at least one deuterium.

In addition, preferably Ar ¹ May be a benzo [c] fluorene group-fluorenyl group, 9,9-diphenyl -9 H-fluorene group or a 7,7-diphenyl -7 H.

In addition, Ar ¹ may be preferably a heterocyclic group of C ₃ -C ₁₂ , more preferably a heterocyclic group of C ₁₂ , and may preferably be a dibenzothienyl group or a dibenzofuryl group. .

Preferably, Ar ² and Ar ³ are independently of each other an aryl group of C ₆ -C ₂₅ , and also preferably an aryl group of C ₆ -C ₁₈ , more preferably C ₆ , C ₁₀ , C ₁₂ , C _It may be an aryl group such as ₁₈ . Specifically, Ar ² and Ar ³ may be independently of each other a phenyl group, naphthyl group, biphenylyl group or terphenylyl group (including p -terphenyl, m -terphenyl, etc.), the phenyl group deuterium, methoxyl, t -May be further substituted with a butyl group or the like.

Also preferably, Ar ² and Ar ³ are each independently a 9,9-dimethyl-9 H -fluorenyl group, a 9,9-diphenyl-9 H -fluorenyl group or a 9,9'-spiro Bifluorenyl group, and the like.

In addition, preferably Ar ² and Ar ³ may be a C ₃ -C ₁₂ heterocyclic group, specifically, a pyrimidyl group, dibenzothienyl, dibenzofuryl group, or the like unsubstituted or substituted with phenyl Can be.

Also, preferably, Ar ² and Ar ³ may be selected independently of each other in the following structure.

Preferably, Ar ¹ to Ar ³ is independently of each other deuterium, halogen, silane group, siloxane group, boron group, germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Of C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of.

In Formula 1, R ¹ and R ² are independently from each other, i) deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; -L'-N (R ^a ) (R ^b ); and combinations thereof, or ii) adjacent groups, ie, adjacent R ¹ , adjacent R ² and / or adjacent R ¹ and R ^{2 may} be bonded to each other to form at least one ring, wherein R ¹ and R ² which do not form a ring are as defined in i). The ring formed by bonding with neighboring groups may be a C ₆ -C ₆₀ aromatic ring, a C ₂ -C ₆₀ hetero ring, a C ₃ -C ₆₀ alicyclic ring, or a fused ring consisting of a combination thereof, It may be a ring or a poly ring, or may be a saturated or unsaturated ring.

In addition, in Formula 1, m is an integer of 0 to 4, n is an integer of 0 to 3, when m is an integer of 2 or more, a plurality of R ¹ may be the same or different from each other, when n is an integer of 2 or more R ^{2 may} also be the same as or different from each other.

Preferably, m = n = 0, or R ¹ may be a C ₆ -C ₁₈ aryl group, a C ₃ -C ₁₀ heterocyclic group, a C ₂ -C ₅ alkenyl group, or the like, and preferably It may be an aryl group of C ₆ , a heterocyclic group of C ₃ , C ₈ , C ₉ , C ₁₀ , or an alkenyl group of C ₃ , specifically, a phenyl group, dibenzothienyl group, triazinyl group, quinolyl group, phenyl Or a substituted or unsubstituted quinazolyl group, propenyl group, and the like.

In addition, preferably, adjacent R ^{1 may} be bonded to each other to form one or two benzene rings to form naphthalene, phenanthrene, etc. together with the benzene rings to which they are bonded.

In addition, preferably, adjacent R ^{2 may} be bonded to each other to form one or two benzene rings to form naphthalene, phenanthrene, etc. together with the benzene ring to which they are bonded.

On the other hand, R ¹ and R ² are independently of each other deuterium, halogen, silane group, siloxane group, boron group, germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Of C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C _20. It may be further substituted with one or more substituents selected from the group consisting of.

In the -L'-N (R ^a ) (R ^b ) of the R ¹ to R ⁴ , L 'is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P, wherein R ^a and R ^b are independent of each other An aryl group of C ₆ -C ₆₀ ; Fluorenyl group; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P.

In Formula 1, when adjacent R ¹ and / or adjacent R ² are bonded to each other to form a ring, it may be represented by any one of the following Formulas 2 to 10. The following Chemical Formulas 2 to 5 are examples of the case where adjacent R ¹ are bonded to each other to form a benzene ring, and the following Chemical Formulas 6 to 9 may be adjacent to each other R ¹ and adjacent R ² to form a benzene ring. An example of one case, Formula 10 is an example of the case where the adjacent R ² are bonded to each other to form a benzene ring.

In Formulas 2 to 10, Ar ¹ to Ar ³ , L, R ¹ , R ² , m and n may be defined in the same manner as defined in Formula 1.

Preferably, in Formula 1, Ar ¹ is

In Formula 1, Formula 1 may be represented by one of Formulas 11 to 20 below. The following Chemical Formulas 12 to 15 are examples of the case where adjacent R ¹ are bonded to each other to form a benzene ring, and the following Chemical Formulas 16 to 19 may be adjacent to each other R ¹ and adjacent R ² to form a benzene ring. An example of one case, Formula 20 is an example of the case where the adjacent R ² are bonded to each other to form a benzene ring.

In Formulas 11 to 20, Ar ² , Ar ³ , L, R ¹ , R ² , m, n, and the like may be defined in the same manner as defined in Formula 1 above.

In addition, in Chemical Formulas 11 to 20, X is O, S or C (R ') (R "), wherein R' and R" are each independently hydrogen; heavy hydrogen; Tritium; Aryl group of C ₆ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; And an alkenyl group of C ₂ -C ₂₀ ; and R ′ and R ″ may be bonded to each other to form a spiro compound together with the carbon to which they are bonded.

In addition, in Formulas 11 to 20, o is an integer of 0 to 4, p is an integer of 0 to 3, R ⁵ and R ⁶ are independently of each other, i) deuterium; Tritium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; And combinations thereof, or ii) adjacent groups may combine with each other to form at least one ring, provided that R ⁵ and R ⁶ which do not form a ring are as defined in i) above. same.

More specifically, the compound represented by Formula 1 to Formula 20 may be any one of the following compounds.

In another embodiment, the present invention provides a compound for an organic electric device represented by Chemical Formula 1.

In another embodiment, the present invention provides an organic electric device containing the compound represented by the formula (1).

In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may include a hole injection layer, a hole transport layer, and an emission auxiliary layer of the organic material layer. Or it may be contained in at least one layer of the light emitting layer. That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer or a light emitting layer. Specifically, it provides an organic electroluminescent device comprising one of the compounds represented by Formula 2 to Formula 10 in the organic material layer, and more specifically, an organic electric comprising one of the compounds represented by Formula 11 to Formula 20 in the organic material layer The present invention provides a device, and more specifically, the present invention provides an organic compound including compounds P1-1 to P1-112, P2-1 to P2-112, and P3-1 to P3-32 represented by the respective chemical formulas in the organic compound layer. Provides an electrical device. In addition, the compound contained in the organic material layer may be one kind or a mixture of two or more represented by the formula (1). For example, the hole transport layer or the light emitting auxiliary layer in the organic material layer may be formed of a P1-1 compound alone, or may include a mixture of P1-1 and P3-1.

In still another embodiment of the present invention, the present invention provides a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric element further comprising.

Hereinafter, the synthesis examples of the compounds represented by the chemical formulas according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

합성예Synthesis Example

Illustratively, the compound according to the present invention (Final Products) is prepared by reacting Sub 1 and Sub 2 as in Scheme 1, but is not limited thereto.

I. Sub 1의 합성예I. Synthesis Example of Sub 1

Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.

1. Sub 1-1의 합성예1. Synthesis Example of Sub 1-1

(1) Sub 1-I-1의 합성(1) Synthesis of Sub 1-I-1

After starting material phenylboronic acid (76.84g, 630.2mmol) was dissolved in THF (2780ml) in a round bottom flask, 4-bromo-1-iodo-2-nitrobenzene (309.96g, 945.3mmol), Pd (PPh ₃ ) ₄ (36.41 g, 31.5 mmol), K ₂ CO ₃ (261.3 g, 1890.6 mmol), water (1390 ml) were added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 122.68 g (yield: 70%) of the product.

(2) Sub 1-II-1의 합성(2) Synthesis of Sub 1-II-1

Sub 1-I-1 (122.68g, 441.1mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (1810ml) in a round bottom flask, triphenylphosphine (289.26g, 1102.8mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give 80.34g (yield: 74%) of the product.

(3) Sub 1-III-1의 합성(3) Synthesis of Sub 1-III-1

Scheme 5

Sub 1-II-1 (80.34g, 326.5mmol) obtained in the above synthesis was dissolved in nitrobenzene (653ml) in a round bottom flask, iodobenzene (99.9g, 489.7mmol), Na ₂ SO ₄ (46.37g, 326.5mmol) , K ₂ CO ₃ (45.12 g, 326.5 mmol), Cu (6.22 g, 97.9 mmol) was added and stirred at 200 ° C. After the reaction was completed, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give 76.78g (yield: 73%) of the product.

(4) Sub 1-IV-1의 합성(4) Synthesis of Sub 1-IV-1

Sub 1-III-1 (76.78 g, 238.3 mmol) obtained in the above synthesis was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (66.57 g, 262.1 mmol), Pd (dppf) Cl ₂ (5.84 g, 7.1 mmol), KOAc (70.16 g, 714.9 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give 73.92g (yield: 84%) of the product.

(5) Sub 1-1의 합성(5) Synthesis of Sub 1-1

Scheme 7

Sub 1-IV-1 (73.92g, 200.2mmol) obtained in the above synthesis was dissolved in THF (880ml) in a round bottom flask, and then 3-bromo-4'-iodo-1,1'-biphenyl (108g, 300.3mmol). ), Pd (PPh ₃ ) ₄ (11.6 g, 10 mmol), K ₂ CO ₃ (83 g, 600.6 mmol) and water (440 mL) were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 63.6g (yield: 67%).

2. Sub 1-7의 합성예2. Synthesis Example of Sub 1-7

(1) Sub 1-I-7의 합성(1) Synthesis of Sub 1-I-7

Scheme 8

Starting material (4- (dibenzo [b, d] thiophen-2-yl) phenyl) boronic acid (95.8g, 315.1mmol), THF (1390ml), 4-bromo-1-iodo-2-nitrobenzene (155g, 472.7 mmol), Pd (PPh ₃ ) ₄ (18.2g, 15.8mmol), K ₂ CO ₃ (130.7g, 945.3mmol), water (695ml) using the synthesis example of Sub 1-I-1 103g (Yield 71%) was obtained.

(2) Sub 1-II-7의 합성(2) Synthesis of Sub 1-II-7

Scheme 9

Sub 1-I-7 (103g, 223.7mmol), o- dichlorobenzene (917ml) and triphenylphosphine (146.7g, 559.3mmol) obtained in the above synthesis were obtained using the synthesis example of Sub 1-II-1, 69g (yield). : 72%).

(3) Sub 1-III-7의 합성(3) Synthesis of Sub 1-III-7

Scheme 10

Sub 1-II-7 (69 g, 161.1 mmol), nitrobenzene (322 ml), iodobenzene (49.4 g, 242 mmol) obtained in the above synthesis, Na ₂ SO ₄ (22.9 g, 161.1 mmol), K ₂ CO ₃ (22.3 g, 161.1 mmol) and Cu (3.1 g, 48.3 mmol) were used to obtain 57 g (yield: 70%) of the product using the synthesis example of Sub 1-III-1.

(4) Sub 1-IV-7의 합성(4) Synthesis of Sub 1-IV-7

Scheme 11

Sub 1-III-7 (57g, 113mmol), DMF (712ml), Bis (pinacolato) diboron (31.6g, 124.3mmol), Pd (dppf) Cl ₂ (2.8g, 3.4mmol), KOAc obtained in the above synthesis (33.3 g, 339 mmol) was obtained using 49.2 g of a product (yield: 79%) using the synthesis example of Sub 1-IV-1.

(5) Sub 1-7의 합성(5) Synthesis of Sub 1-7

Scheme 12

Sub 1-IV-7 (49.2 g, 89.2 mmol) obtained in the above synthesis was dissolved in THF (392 ml) in a round bottom flask, followed by 3-bromo-4'-iodo-1,1'-biphenyl (48.1 g, 134 mmol). ), Pd (PPh ₃ ) ₄ (5.2g, 4.5mmol), K ₂ CO ₃ (37g, 268mmol), water (196ml) using the synthesis example of Sub 1-1, the product 40.4g (yield: 69% )

3. Sub 1-13의 합성3. Synthesis of Sub 1-13

(1) Sub 1-III-13의 합성(1) Synthesis of Sub 1-III-13

Scheme 13

Sub 1-II-1 (70g, 284.4mmol) obtained from the above synthesis, dissolved with nitrobenzene (570ml), 2-iodo-9,9-diphenyl-9H-fluorene (189.6g, 426.7mmol), Na ₂ SO ₄ (40.4g, 284.4mmol), K ₂ CO ₃ (39.3g, 284.4mmol), Cu (5.42g, 85.3mmol), using the synthesis example of Sub 1-III-1, product 108.8g (yield: 68% )

(2) Sub 1-IV-13의 합성(2) Synthesis of Sub 1-IV-13

Scheme 14

Sub 1-III-13 (108.8g, 193.4mmol), DMF (1220ml), Bis (pinacolato) diboron (54.0g, 212.76mmol), Pd (dppf) Cl ₂ (4.73g, 5.8mmol) obtained in the above synthesis, KOAc (56.94 g, 580.3 mmol) was obtained by the synthesis example of Sub 1-IV-1, which obtained 86.1 g (yield: 73%) of product.

(3) Sub 1-13의 합성(3) Synthesis of Sub 1-13

Scheme 15

Sub 1-IV-13 (86.1 g, 141.2 mmol), THF (620 ml), 3-bromo-4'-iodo-1,1'-biphenyl (76.1 g, 211.9 mmol) obtained in the above synthesis, Pd (PPh ₃ ) ₄ (8.2 g, 7.06 mmol), K ₂ CO ₃ (58.6 g, 423.7 mmol), and water (310 ml) were obtained using 68.6 g (yield: 68%) of the product using the synthesis example of Sub 1-1.

4. Sub 1-14의 합성4.Synthesis of Sub 1-14

(1) Sub 1-III-14의 합성(1) Synthesis of Sub 1-III-14

Scheme 16

Sub 1-II-1 (63 g, 255.9 mmol), nitrobenzene (512 ml), 3-iodo-9,9-diphenyl-9H-fluorene (170.6 g, 383.9 mmol), Na ₂ SO ₄ (36.4 g) , 256 mmol), K ₂ CO ₃ (35.4 g, 256 mmol) and Cu (4.88 g, 76.8 mmol) were obtained using the synthesis example of Sub 1-III-1 to obtain 99.3 g (yield: 69%) of product.

(2) Sub 1-IV-14의 합성(2) Synthesis of Sub 1-IV-14

Scheme 17

Sub 1-III-14 (99.3 g, 193.4 mmol), DMF (1110 ml), Bis (pinacolato) diboron (49.3 g, 194.2 mmol) obtained in the above synthesis, Pd (dppf) Cl ₂ (4.32 g, 5.3 mmol), KOAc (52g, 529.6mmol) was obtained using the synthesis example of Sub 1-IV-1, to give 80.7g (yield: 75%) of product.

(3) Sub 1-14의 합성(3) Synthesis of Sub 1-14

Scheme 18

Sub 1-IV-14 (80.7g, 132.3mmol), THF (582ml), 3-bromo-4'-iodo-1,1'-biphenyl (71.3g, 198.6mmol) obtained in the above synthesis, Pd (PPh ₃ ) ₄ (7.65 g, 6.62 mmol), K ₂ CO ₃ (54.9 g, 397.2 mmol) and water (291 ml) were obtained using 62.4 g (yield: 66%) of the product using the synthesis example of Sub 1-1.

5. Sub 1-17의 합성5. Synthesis of Sub 1-17

(1) Sub 1-III-17의 합성(1) Synthesis of Sub 1-III-17

Scheme 19

Sub 1-II-1 (60g, 244mmol), nitrobenzene (487ml), 5'-iodo-1,1 ': 3', 1 ''-terphenyl (130.3g, 365.7mmol) obtained from the above synthesis, Na ₂ SO ₄ (34.6g, 244mmol), K ₂ CO ₃ (33.7g, 244mmol), Cu (4.65g, 73.1mmol) was obtained using the synthesis example of Sub 1-III-1 82.1g (yield: 71%) Got.

(2) Sub 1-IV-17의 합성(2) Synthesis of Sub 1-IV-17

Scheme 20

Sub 1-III-17 (82.1 g, 173.1 mmol), DMF (1090 ml), Bis (pinacolato) diboron (48.3 g, 190.4 mmol), Pd (dppf) Cl ₂ (4.24 g, 5.2 mmol) obtained in the above synthesis, KOAc (51 g, 519.2 mmol) was obtained by the synthesis example of Sub 1-IV-1, 65.9 g (yield: 73%) of the product.

(3) Sub 1-17의 합성(3) Synthesis of Sub 1-17

Scheme 21

Sub 1-III-17 (82.1 g, 173.1 mmol), DMF (1090 ml), Bis (pinacolato) diboron (48.3 g, 190.4 mmol), Pd (dppf) Cl ₂ (4.24 g, 5.2 mmol) obtained in the above synthesis, KOAc (51g, 519.2mmol) was used to obtain the product 65.9g (yield: 73%) using the synthesis example of Sub 1-IV-1.

6. Sub 1-32의 합성 6.Synthesis of Sub 1-32

(1) Sub 1-I-32의 합성(1) Synthesis of Sub 1-I-32

Scheme 22

Starting materials naphthalen-1-ylboronic acid (70g, 407mmol), THF (1790ml), 4-bromo-1-iodo-2-nitrobenzene (200g, 610.5mmol), Pd (PPh ₃ ) ₄ (23.5g, 20.35mmol ), K ₂ CO ₃ (168.8 g, 1221 mmol) and water (895 ml) were obtained using 94.8 g (yield: 71%) of the product using the synthesis example of Sub 1-I-1.

(2) Sub 1-II-32의 합성(2) Synthesis of Sub 1-II-32

Scheme 23

Sub 1-I-32 (94.8g, 288.9mmol), o- dichlorobenzene (1184ml), triphenylphosphine (189.4g, 722.2mmol) obtained in the above synthesis was obtained using the synthesis example of Sub 1-II-1, 61.2g. (Yield 75%) was obtained.

(3) Sub 1-III-32의 합성(3) Synthesis of Sub 1-III-32

Scheme 24

Sub 1-II-32 (61.2 g, 206.6 mmol), nitrobenzene (413 ml), 2-iodo-9,9-diphenyl-9H-fluorene (137.7 g, 310 mmol), Na ₂ SO ₄ (29.35 g) obtained in the above synthesis , 206.6 mmol), K ₂ CO ₃ (28.6 g, 206.6 mmol) and Cu (3.9 g, 62 mmol) were obtained using the synthesis examples of Sub 1-III-1 to give 89.86 g (yield: 71%) of the product.

(4) Sub 1-IV-32의 합성(4) Synthesis of Sub 1-IV-32

Scheme 25

Sub 1-III-32 (89.86 g, 146.7 mmol), DMF (924 ml), Bis (pinacolato) diboron (41 g, 161.4 mmol), Pd (dppf) Cl ₂ (3.59 g, 4.4 mmol), KOAc obtained in the above synthesis (43.2 g, 440.1 mmol) was obtained by using the synthesis example of Sub 1-IV-1, 74.5 g (yield: 77%) of the product.

(5) Sub 1-32의 합성(5) Synthesis of Sub 1-32

Scheme 26

Sub 1-IV-32 (74.5 g, 112.9 mmol) obtained in the above synthesis was dissolved in THF (496 ml) in a round bottom flask, followed by 3-bromo-4'-iodo-1,1'-biphenyl (60.8 g, 169.4 mmol), Pd (PPh ₃ ) ₄ (6.53g, 5.65mmol), K ₂ CO ₃ (46.8g, 338.8mmol), water (248ml) using the synthesis example of Sub 1-1 above, product 59.6g (yield) : 69%).

7. 1-34의 합성 7. Synthesis of 1-34

(1) Sub 1-I-34의 합성(1) Synthesis of Sub 1-I-34

Scheme 27

Starting materials naphthalen-2-ylboronic acid (70g, 407mmol), THF (1790ml), 4-bromo-1-iodo-2-nitrobenzene (200g, 610.5mmol), Pd (PPh ₃ ) ₄ (23.5g, 20.35mmol ), K ₂ CO ₃ (168.8 g, 1221 mmol), and water (895 ml) were obtained using a synthesis example of Sub 1-I-1 to obtain 97.5 g (yield: 73%) of product.

(2) Sub 1-II-34의 합성(2) Synthesis of Sub 1-II-34

Scheme 28

Sub 1-I-34 (97.5g, 297.1mmol), o- dichlorobenzene (1220ml) and triphenylphosphine (194.8g, 742.8mmol) obtained in the above synthesis were used to synthesize 65.1g of Sub 1-II-1. (Yield 74%) was obtained.

(3) Sub 1-III-34의 합성(3) Synthesis of Sub 1-III-34

Scheme 29

Sub 1-II-34 (65.1 g, 220 mmol), nitrobenzene (440 ml), 3-iodo-9,9-diphenyl-9H-fluorene (146.5 g, 330 mmol), Na ₂ SO ₄ (31.2 g, 220 mmol), K ₂ CO ₃ (30.4 g, 220 mmol) and Cu (4.2 g, 66 mmol) were obtained using the synthesis example of Sub 1-III-1 to obtain 95.6 g (yield: 71%) of product.

(4) Sub 1-IV-34의 합성(4) Synthesis of Sub 1-IV-34

Scheme 30

Sub 1-III-34 (95.6 g, 156.1 mmol) obtained in the above synthesis was dissolved in DMF (980 ml) in a round bottom flask, followed by Bis (pinacolato) diboron (43.6 g, 171.7 mmol), Pd (dppf) Cl ₂ ( 3.82 g, 4.7 mmol), KOAc (46 g, 468.2 mmol) was obtained using the synthesis example of Sub 1-IV-1 to obtain 77.2 g (yield: 75%) of product.

(5) Sub 1-34의 합성(5) Synthesis of Sub 1-34

Scheme 31

Sub 1-IV-34 (77.2 g, 117 mmol), THF (510 ml), 3-bromo-4'-iodo-1,1'-biphenyl (63 g, 175.6 mmol), Pd (PPh ₃ ) ₄ obtained in the above synthesis (6.76 g, 5.85 mmol), K ₂ CO ₃ (48.5 g, 351 mmol) and water (255 ml) were obtained using 58.2 g (yield: 65%) of the product using the synthesis example of Sub 1-1.

8. 1-35의 합성 8. Synthesis of 1-35

(1) Sub 1-I-35의 합성(1) Synthesis of Sub 1-I-35

Scheme 32

Starting materials phenanthren-9-ylboronic acid (70g, 315.2mmol), THF (1388ml), 4-bromo-1-iodo-2-nitrobenzene (155.1g, 472.9mmol), Pd (PPh ₃ ) ₄ (18.2g, 15.8 mmol), K ₂ CO ₃ (130.7 g, 945.7 mmol) and water (694 ml) were obtained using the synthesis example of Sub 1-I-1 to obtain 85.8 g (yield: 72%) of the product.

(2) Sub 1-II-35의 합성(2) Synthesis of Sub 1-II-35

Scheme 33

Sub 1-I-35 (85.8g, 226.9mmol), o- dichlorobenzene (930ml) and triphenylphosphine (148.8g, 567.1mmol) obtained in the above synthesis were obtained using the synthesis example of Sub 1-II-1 60.5g. (Yield 77%) was obtained.

(3) Sub 1-III-35의 합성(3) Synthesis of Sub 1-III-35

Scheme 34

Sub 1-II-35 (60.5 g, 174.7 mmol), nitrobenzene (350 ml), 3-iodo-9,9-diphenyl-9H-fluorene (116.5 g, 262.1 mmol), Na ₂ SO ₄ (24.8) g, 174.7 mmol), K ₂ CO ₃ (24.2 g, 174.7 mmol), Cu (3.33 g, 52.4 mmol) were obtained using 84.5 g (yield: 73%) of the product using the synthesis example of Sub 1-III-1. Got it.

(4) Sub 1-IV-35의 합성(4) Synthesis of Sub 1-IV-35

Scheme 35

Sub 1-III-35 (84.5 g, 127.5 mmol) obtained in the above synthesis, DMF (854 ml), Bis (pinacolato) diboron (35.6 g, 140.3 mmol), Pd (dppf) Cl ₂ (3.12 g, 3.82 mmol), KOAc (37.5g, 382.5mmol) was obtained using the synthesis example of Sub 1-IV-1 to give 70.6g (yield: 78%) of product.

(5) Sub 1-35의 합성(5) Synthesis of Sub 1-35

Scheme 36

Sub 1-IV-35 (70.6 g, 99.5 mmol) obtained in the above synthesis was dissolved in THF (438 ml) in a round bottom flask, followed by 3-bromo-4'-iodo-1,1'-biphenyl (53.6 g, 149.2 mmol), Pd (PPh ₃ ) ₄ (5.75g, 4.97mmol), K ₂ CO ₃ (41.2g, 298.4mmol), water (219ml) using the synthesis example of Sub 1-1, product 55.1g (yield) : 68%).

9. Sub 1-44의 합성9.Synthesis of Sub 1-44

(1) Sub 1-III-44의 합성(1) Synthesis of Sub 1-III-44

Scheme 37

Sub 1-II-1 (60 g, 244 mmol), nitrobenzene (487 ml), 2-iododibenzo [b, d] furan (107.6 g, 365.7 mmol) obtained in the above synthesis, Na ₂ SO ₄ (34.6 g, 244 mmol), K 68.4 g (yield: 68%) of ₂ CO ₃ (33.7 g, 244 mmol) and Cu (4.65 g, 73.1 mmol) were obtained using the synthesis examples of Sub 1-III-1.

(2) Sub 1-IV-44의 합성(2) Synthesis of Sub 1-IV-44

Scheme 38

Sub 1-III-44 (68.4g, 166mmol), DMF (1045ml), Bis (pinacolato) diboron (46.3g, 182.5mmol), Pd (dppf) Cl ₂ (4.06g, 5mmol), KOAc obtained in the above synthesis (48.8 g, 497.7 mmol) was obtained using the synthesis example of Sub 1-IV-1 to give 56.4 g (yield: 74%) of product.

(3) Sub 1-44의 합성(3) Synthesis of Sub 1-44

Scheme 39

Sub 1-IV-44 (56.4 g, 122.8 mmol), THF (540 ml), 3-bromo-4'-iodo-1,1'-biphenyl (66.1 g, 184 mmol) obtained in the above synthesis, Pd (PPh ₃ ) ₄ (7.1 g, 6.14 mmol), K ₂ CO ₃ (50.9 g, 368.4 mmol) and water (270 ml) were obtained using 47.8 g (yield: 69%) of the product using the synthesis example of Sub 1-1.

10. Sub 1-54의 합성10. Synthesis of Sub 1-54

(1) Sub 1-III-54의 합성(1) Synthesis of Sub 1-III-54

Scheme 40

Sub 1-II-1 (50 g, 203.2 mmol), nitrobenzene (406 ml), 4-iodo-1,1'-biphenyl (85.4 g, 304.7 mmol) obtained in the above synthesis, Na ₂ SO ₄ (28.9 g, 203.2 mmol) ), K ₂ CO ₃ (28.1 g, 203.2 mmol) and Cu (3.87 g, 61 mmol) were obtained using the synthesis examples of Sub 1-III-1 to give 54.2 g (yield: 68%) of the product.

(2) Sub 1-IV-54의 합성(2) Synthesis of Sub 1-IV-54

Scheme 41

Sub 1-III-54 (54.2 g, 136.1 mmol), DMF (857 ml), Bis (pinacolato) diboron (38.0 g, 150 mmol), Pd (dppf) Cl ₂ (3.33 g, 4.1 mmol), KOAc obtained in the above synthesis (40.1 g, 408 mmol) was obtained using the synthesis example of Sub 1-IV-1 to 42.4 g (yield: 70%) of the product.

(3) Sub 1-54의 합성(3) Synthesis of Sub 1-54

Scheme 42

Sub 1-IV-54 (42.4g, 95.2mmol), THF (418ml), 2-bromo-4'-iodo-1,1'-biphenyl (51.3g, 142.8mmol) obtained in the above synthesis, Pd (PPh ₃ ) ₄ (5.5 g, 4.76 mmol), K ₂ CO ₃ (39.5 g, 285.6 mmol), and water (209 ml) were obtained using the synthesis example of Sub 1-1 to obtain 34.1 g (yield: 65%) of the product.

11. Sub 1-66의 합성11.Synthesis of Sub 1-66

(1) Sub 1-III-66의 합성(1) Synthesis of Sub 1-III-66

Scheme 43

Sub 1-II-1 (50 g, 203.2 mmol), nitrobenzene (406 ml), 1-iodo-9,9-diphenyl-9H-fluorene (135.4 g, 305 mmol), Na ₂ SO ₄ (28.9 g, 203.2 mmol), K ₂ CO ₃ (28.1 g, 203.2 mmol) and Cu (3.87 g, 61 mmol) were obtained using the synthesis examples of Sub 1-III-1 to obtain 70.9 g (yield: 62%) of the product.

(2) Sub 1-IV-66의 합성(2) Synthesis of Sub 1-IV-66

Scheme 44

Sub 1-III-66 (70.9g, 126mmol), DMF (794ml), Bis (pinacolato) diboron (35.2g, 138.7mmol), Pd (dppf) Cl ₂ (3.09g, 3.78mmol), KOAc obtained in the above synthesis (37.11 g, 378.1 mmol) was obtained using the synthesis example of Sub 1-IV-1 to give 51.5 g (yield: 67%) of product.

(3) Sub 1-66의 합성(3) Synthesis of Sub 1-66

Scheme 45

Sub 1-IV-66 (51.5g, 84.5mmol), THF (370ml), 2-bromo-4'-iodo-1,1'-biphenyl (45.5g, 126.7mmol) obtained in the above synthesis, Pd (PPh ₃ ) ₄ (4.88 g, 4.22 mmol), K ₂ CO ₃ (35.03 g, 253.5 mmol) and water (185 ml) were obtained using 36.2 g (yield: 60%) of the product using the synthesis example of Sub 1-1.

Meanwhile, examples of Sub 1 according to the synthesis example are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.

(4) Sub 1-148의 합성(4) Synthesis of Sub 1-148

Scheme 46

Sub 1-IV-11 (31.2 g, 84.5 mmol) obtained in the above synthesis, 370 mL of THF, 3-bromo-2'-iodo-1,1 ': 4', 1 ''-terphenyl (55.1g, 126.7 mmol ), Pd (PPh ₃ ) ₄ (4.88 g, 4.22 mmol), K ₂ CO ₃ (35.03 g, 253.5 mmol), and 185 mL of water were tested in the same manner as in the Sub-1-1 experiment. : 68%).

TABLE 1

II. Sub 2의 합성예II. Synthesis Example of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 46, but is not limited thereto.

Scheme 47

1. Sub 2-1의 합성1.Synthesis of Sub 2-1

Scheme 48

Bromobenzene (37.1g, 236.2mmol) was added to a round bottom flask and dissolved with toluene (2200ml), aniline (20g, 214.8mmol), Pd ₂ (dba) ₃ (9.83g, 10.7mmol), P ( t -Bu) ₃ (4.34 g, 21.5 mmol) and NaO t -Bu (62 g, 644.3 mmol) were added in this order and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product 28g (yield: 77%).

2. Sub 2-3의 합성2. Synthesis of Sub 2-3

Scheme 49

3-bromo-1,1'-biphenyl (55.1g, 236.2mmol), aniline (20g, 214.8mmol), Pd ₂ (dba) ₃ (9.83g, 10.7mmol), P ( t -Bu) ₃ (4.34g , 21.5 mmol), NaO t -Bu (62 g, 644.3 mmol) and toluene (2200 ml) were obtained using the synthesis example of Sub 2-1 to obtain 41.1 g (yield: 78%) of the product.

3. Sub 2-4의 합성3. Synthesis of Sub 2-4

Scheme 50

4-bromo-1,1'-biphenyl (37.88g, 162.5mmol), [1,1'-biphenyl] -4-amine (25g, 147.7mmol), Pd ₂ (dba) ₃ (6.76g, 7.4mmol) , P ( t -Bu) ₃ (3 g, 14.8 mmol), NaO t -Bu (66.62 g, 693.2 mmol) and toluene were obtained using 35.6 g (yield: 75%) of the product using the synthesis example of Sub 2-1. Got it.

4. Sub 2-7의 합성4. Synthesis of Sub 2-7

Scheme 51

2-bromonaphthalene (39.8g, 192.1mmol), naphthalen-1-amine (25g, 174.6mmol), Pd ₂ (dba) ₃ (8.0g, 8.73mmol), P ( t -Bu) ₃ (3.53g, 17.5mmol ), NaO t -Bu (50.3 g, 523.8 mmol) and toluene (1800 ml) were obtained using the Sub 2-1 synthesis example to obtain 36.2 g (yield: 77%) of the product.

5. Sub 2-9의 합성5. Synthesis of Sub 2-9

Scheme 52

2-bromo-9,9-diphenyl-9 H -fluorene (93.9g, 236.2mmol), toluene (2250ml), aniline (20g, 214.8mmol), Pd ₂ (dba) ₃ (9.83g, 10.7mmol), P ( T -Bu) ₃ (4.34 g, 21.5 mmol) and NaO t -Bu (62 g, 644.3 mmol) were obtained using the synthesis examples of Sub 2-1 to obtain 63.3 g (yield: 72%) of the product.

6. Sub 2-12의 합성6.Synthesis of Sub 2-12

Scheme 53

2-bromo-9,9-diphenyl-9 H -fluorene (64.6g, 162.5mmol), toluene (1550ml), [1,1'-biphenyl] -4-amine (25g, 147.7mmol), Pd ₂ (dba ) ₃ (6.76 g, 162.5 mmol), P ( t -Bu) ₃ (3 g, 14.8 mmol), NaO t -Bu (42.6 g, 443.2 mmol) using a synthesis example of Sub 2-1, product 53.8 g (Yield 75%) was obtained.

7. Sub 2-13의 합성7.Synthesis of Sub 2-13

Scheme 54

3-bromodibenzo [b, d] thiophene (42.8g, 162.5mmol), toluene (1550ml), [1,1'-biphenyl] -4-amine (25g, 147.7mmol), Pd ₂ (dba) ₃ (6.76g , 162.5 mmol), P ( t -Bu) ₃ (3 g, 14.8 mmol), NaO t -Bu (42.6 g, 443.2 mmol) using the Sub 2-1 synthesis example, 37.9 g (yield: 73% )

8. Sub 2-17의 합성8. Synthesis of Sub 2-17

Scheme 55

1-bromo-4-methoxybenzene (36g, 192.1mmol), naphthalen-1-amine (25g, 174.6mmol), Pd ₂ (dba) ₃ (8.0g, 8.73mmol), P ( t -Bu) ₃ (3.53g , 17.5 mmol), NaO t -Bu (50.3 g, 523.8 mmol) and toluene (1800 ml) were obtained using the synthesis example of Sub 2-1 to give 32.2 g (yield: 74%) of the product.

9. Sub 2-26의 합성9.Synthesis of Sub 2-26

Scheme 56

5'-bromo-1,1 ': 3', 1 ''-terphenyl (73.04g, 236.2mmol), amine (20g, 214.8mmol), Pd ₂ (dba) ₃ (9.83g, 10.7mmol), P ( t- Bu) ₃ (4.34 g, 21.5 mmol), NaO t -Bu (62 g, 644.3 mmol) and toluene (2250 ml) were obtained using 49 g (yield: 71%) of the product using the synthesis example of Sub 2-1. .

Meanwhile, examples of Sub 2 according to the synthesis example are as follows, but are not limited thereto, and their FD-MSs are shown in Table 2 below.

TABLE 2

III. 최종생성물(Final Products)의 합성예III. Synthesis Example of Final Products

Sub 2 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 1 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), P ( t -Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain final products.

1. Product P1-1의 합성1.Synthesis of Product P1-1

Scheme 57

Sub 2-1 (8g, 47.3mmol) was added to a round bottom flask and dissolved with toluene (500ml), then Sub 1-1 (24.7g, 52.0mmol), Pd ₂ (dba) ₃ (2.2g, 2.4mmol), P ( t- Bu) ₃ (1 g, 4.73 mmol) and NaO t -Bu (13.6 g, 141.8 mmol) were added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 20.2g (yield: 76%) of the product.

2. Product P1-4의 합성2. Synthesis of Product P1-4

Scheme 58

Sub 2-4 (8g, 24.9mmol) to Sub 1-1 (13g, 27.4mmol), Pd ₂ (dba) ₃ (1.14g, 1.24mmol), P ( t -Bu) ₃ (0.5g, 2.49mmol) , NaO t -Bu (7.17 g, 74.7 mmol) and toluene (265 ml) were obtained using 13 g of a product (yield: 73%) using the synthesis example of Product P1-1.

3. Product P1-8의 합성3. Synthesis of Product P1-8

Scheme 59

Sub 2-9 (10g, 24.4mmol) to Sub 1-1 (12.7g, 26.9mmol), Pd ₂ (dba) ₃ (1.12g, 1.22mmol), P ( t -Bu) ₃ (0.5g, 2.44mmol) ), NaO t -Bu (7.04 g, 73.3 mmol) and toluene (260 ml) were used to obtain 15.1 g (yield: 77%) of the product using the synthesis example of Product P1-1.

4. Product P1-17의 합성4. Synthesis of Product P1-17

Scheme 60

Sub 2-13 (10g, 28.5mmol) to Sub 1-4 (16.4g, 31.3mmol), Pd ₂ (dba) ₃ (1.3g, 1.42mmol), P ( t -Bu) ₃ (0.6g, 2.85mmol) ), NaO t -Bu (8.2 g, 85.4 mmol) and toluene (300 ml) were obtained using 16.1 g (yield: 71%) of the product using the synthesis example of Product P1-1.

5. Product P2-49의 합성5. Synthesis of Product P2-49

Scheme 61

Sub 2-6 (10g, 37.13mmol) to Sub 1-65 (29.2g, 40.84mmol), Pd ₂ (dba) ₃ (1.7g, 1.9mmol), P ( t -Bu) ₃ (0.8g, 3.7mmol ), NaO t -Bu (10.7 g, 111.4 mmol) and toluene (390 ml) were obtained using 25.1 g (yield: 75%) of the product using the synthesis example of Product P1-1.

6. Product P2-77의 합성6.Synthesis of Product P2-77

Scheme 62

Sub 2-1 (8 g, 47.3 mmol) to Sub 1-68 (32.6 g, 52 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.4 mmol), P ( t -Bu) ₃ (1 g, 4.73 mmol), NaO t -Bu (13.6 g, 141.8 mmol) and toluene (500 ml) were obtained using 23.7 g (yield: 70%) of the product using the synthesis example of Product P1-1.

On the other hand, FD-MS of the compounds P1-1 to P2-112 of the present invention prepared according to the synthesis examples as shown in Table 3 below.

(7) Product P3-3 합성(7) Product P3-3 Synthesis

Scheme 63

Sub 1-103 (26.0 g, 47.3 mmol) in Sub 2-13 (18.3 g, 52 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.4 mmol), P ( t -Bu) ₃ (1 g, 4.73 mmol), NaO t -Bu (13.6 g, 141.8 mmol) and toluene (500 mL) were obtained using the Product P1-1 synthesis method to obtain 22.9 g (yield: 59%) of the product.

(8) Product P3-23 합성(8) Product P3-23 Synthesis

Scheme 64

Sub 1-111 (26.0 g, 47.3 mmol) in Sub 2-10 (25.1 g, 52 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.4 mmol), P ( t -Bu) ₃ (1 g, 4.73 mmol), NaO t -Bu (13.6 g, 141.8 mmol) and toluene (500 mL) were obtained using the Product P1-1 synthesis method to obtain 29.3 g (yield: 65%) of the product.

(9) Product P3-17 합성(9) Product P3-17 Synthesis

Scheme 65

Sub 1-104 (26.0 g, 47.3 mmol) in Sub 2-1 (8.8 g, 52 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.4 mmol), P ( t -Bu) ₃ (1 g, 4.73 mmol), NaO t -Bu (13.6 g, 141.8 mmol) and toluene (500 mL) were obtained using the Product P1-1 synthesis to give 19.9 g (yield: 66%) of the product.

(10) Product P3-32 합성(10) Product P3-32 Synthesis

Scheme 66

Sub 1-154 (33.2g, 47.3 mmol) in Sub 2-1 (8.8g, 52 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.4 mmol), P ( t -Bu) ₃ (1 g, 4.73 mmol), NaO t -Bu (13.6 g, 141.8 mmol) and toluene (500 mL) were obtained using the Product P1-1 synthesis to give 21.7 g (yield: 58%) of product.

TABLE 3

유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device

[실시예 1] 정공수송층(그린)Example 1 Hole Transport Layer (Green)

An organic electroluminescent device was manufactured 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) formed on the organic substrate. After the hole injection layer was formed, Compound P1-1 of the present invention was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as "CBP") is used as a host material on the hole transport layer, and tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ ). And a dopant material, and then doped at a weight ratio of 90:10 to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited on the light emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and tris (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[실시예 2] 내지 [실시예 256] 정공수송층(그린)[Example 2] to [Example 256] hole transport layer (green)

Instead of the compound P1-1 of the present invention as the hole transporting material, one of the compounds of the present invention P1-2 to P1-112, P2-1 to P2-112 and P3-1 to P3-32 shown in Table 4 was used. Except for the organic electroluminescent device was manufactured in the same manner as in Example 1.

[비교예 1]Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used instead of Compound P1-1 of the present invention as a hole transport layer material.

[비교예 2]Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used instead of Compound P1-1 of the present invention as a hole transport layer material.

Comparative Compound 2

[비교예 3]Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 was used instead of Compound P1-1 of the present invention as a hole transport layer material.

Comparative Compound 3

[비교예 4][Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 4 was used instead of Compound P1-1 of the present invention as a hole transport layer material.

Comparative Compound 4

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 224 and Comparative Examples 1 to 4 of the present invention The T95 lifetime was measured using a life measurement instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 4 below.

TABLE 4

As can be seen in Table 4, the organic electroluminescent device using the compound of the present invention as a material of the hole transport layer is significantly higher than the organic electroluminescent device using comparative compound 1 having a different structure from the compound of the present invention as the material of the hole transport layer It can be seen that the high efficiency and long life.

In addition, when the organic electroluminescent device using Comparative Compounds 2 to 4 using carbazole as a mother nucleus as the material of the hole transport layer, as in the compound of the present invention, a device to which a linking group is bonded to Carbazole No. 3 (Comparative Example 2 ) Was slightly lower in efficiency than the device (comparative example 3, comparative example 4) to which the linking group is bonded to carbazole No. 2, but it showed a relatively long life, and the comparative example of the non-linear structure of the connecting group It was confirmed that the device exhibits higher efficiency than the device of Comparative Example 3 in which a linear linking group is bonded to carbazole No. 2.

Finally, the results of Table 4 show that the biphenyl, which is a linking group, is linearly bonded to the carbazole derivative, and the amine group is bonded to the meta and ortho positions of the biphenyl structure, which is a linking group. The device using the compound of the present invention as a material for the hole transport layer is higher than the device of Comparative Example 4 in which the amine group is bonded to the para position in a biphenyl structure in which the linking group is non-linear. It can confirm that efficiency is shown.

In addition, in the compound form of the present invention, P2 forms (P2-1 to P2-112; linker biphenyls) than P1 forms (P1-1 to P1-112; amine groups bonded to the meta position of the linker biphenyl) A tendency to show higher efficiency and longer lifespan of amine groups bonded to ortho positions).

The above result shows that the conjugation length is shorter than when the carbazole is connected to position 3 as the connector is connected to position 2 of the carbazole, which results in a wider band gap. It has a HOMO value, and when the amine group is bonded to the meta or ortho position rather than the para position, the bonding angle becomes smaller, which results in a higher T1 value, thereby improving the electron blocking ability. As a result, the exciton is more easily generated in the light emitting layer, and thus, the efficiency is improved and the life is long.

Taking the above characteristics (deep HOMO energy level, high T1 value, thermal stability) into account, the band gap, electrical properties, and interfacial properties can be greatly changed depending on the bonding position of carbazole and amine group. It can be seen that this is a major factor in improving device performance.

In addition, in the case of the hole transport layer, it is necessary to grasp the interrelationship with the light emitting layer (host), and even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics indicated in the hole transport layer in which the compound according to the present invention is used. .

[실시예 257] 발광보조층(레드)Example 257 Light-emitting auxiliary layer (red)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer is formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then N, N'-Bis (1-naphthalenyl) -N on the hole injection layer. , N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Next, after the vacuum deposition of compound P1-1 of the invention on the hole transport layer to a thickness of 20nm to form a light-emitting auxiliary layer, the CBP in the light emitting layer to the secondary host _{material, (piq) 2 Ir (acac} ) [ Bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] was doped with a dopant material at a weight of 95: 5 to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting 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 transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[실시예 258 내지 [실시예 346] 발광보조층(레드)[Example 258 to [Example 346] light emitting auxiliary layer (red)

Compound P1-2 to P1-16, P1-63, P1-64, P1-101 to P1-108, P2-1 to the compound of the present invention shown in Table 5 below instead of the compound P1-1 of the present invention as a light emitting auxiliary layer material. An organic light emitting diode device was manufactured according to the same method as Example 257 except for using one of P2-20, P2-45 to P2-52, P2-61 to P2-64, P3-1 to P3-32. It was.

[비교예 5][Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 257, except that Comparative Compound 2 was used instead of Compound P1-1 of the present invention as a light-emitting auxiliary layer material.

[비교예 6]Comparative Example 6

An organic electroluminescent device was manufactured in the same manner as in Example 257, except that Comparative Compound 3 was used instead of Compound P1-1 of the present invention as a light-emitting auxiliary layer material.

[비교예 7]Comparative Example 7

An organic electroluminescent device was manufactured in the same manner as in Example 257, except that Comparative Compound 4 was used instead of Compound P1-1 of the present invention as a light emitting auxiliary layer material.

[비교예 8]Comparative Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 257, except that an emission auxiliary layer was not formed.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 257 to 346 and Comparative Examples 5 to 8 of the present invention The T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at 2500 cd / m 2 reference luminance. The measurement results are shown in Table 5 below.

TABLE 5

[실시예 351] 발광보조층(그린)[Example 351] Light-emitting auxiliary layer (green)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then a NPD was vacuum deposited with a thickness of 60 nm on the hole injection layer to form a hole transport layer. . Subsequently, the compound P1-21 of the present invention is vacuum-deposited on the hole transport layer to form a light emitting auxiliary layer by vacuum deposition at a thickness of 20 nm, and then CBP is a host material and Ir (ppy) ₃ is a dopant material on the light emitting auxiliary layer. Doped at a weight ratio of 95: 5 to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer was formed by vacuum depositing Alq ₃ to a thickness of 40 nm on the hole blocking layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[실시예 352] 내지 [실시예 390] 발광보조층(그린)[Example 352] to [Example 390] Light emitting auxiliary layer (green)

Instead of compound P1-21 of the present invention as the light emitting auxiliary layer material, one of the compounds P1-22 to P1-38, P3-1 to P3-10, and P3-17 to P3-28 of the present invention shown in Table 6 below was used. An organic electroluminescent device was manufactured in the same manner as in Example 351 except for the above-mentioned points.

[비교예 9]Comparative Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 351, except that Comparative Compound 2 was used instead of Compound P1-21 of the present invention as a light emitting auxiliary layer material.

[비교예 10]Comparative Example 10

An organic electroluminescent device was manufactured in the same manner as in Example 351, except that Comparative Compound 3 was used instead of Compound P1-21 of the present invention as a light emitting auxiliary layer material.

[비교예 11]Comparative Example 11

An organic electroluminescent device was manufactured in the same manner as in Example 351, except that Comparative Compound 4 was used instead of Compound P1-21 of the present invention as a light emitting auxiliary layer material.

[비교예 12]Comparative Example 12

An organic electroluminescent device was manufactured in the same manner as in Example 351, except that an emission auxiliary layer was not formed.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 351 to 390 and Comparative Examples 9 to 12 of the present invention T95 life was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 6 below.

TABLE 6

As can be seen from the results of Table 5 and Table 6, the organic electroluminescent device using the compound of the present invention as a material of the light emitting auxiliary layer is an organic electroluminescent device that does not form a light emitting auxiliary layer and the comparative compounds 2 to 4 It can be seen that the efficiency and lifespan are improved compared to the organic electroluminescent device used as the material of the layer, and in particular, the device using the compound of the present invention as the light emitting auxiliary layer in comparison with the device not using the light emitting auxiliary layer (Comparative Example 12). It can be seen that exhibits significantly high efficiency and long life.

In addition, even when the linking group (substituted with an amine group) is bonded at the carbazole No. 2 position, it can be seen that the amine group shows a big difference in life depending on which position of the linking group.

This may be due to the difference in bonding angle depending on which position of the amine group is bonded, resulting in a difference in T1 value resulting in a difference in electron blocking ability.

In addition, referring to Tables 5 and 6, in the compounds of the present invention, compounds in which R ³ or R ⁴ is substituted with a substituent other than hydrogen (P3-1 to P3-32) are red and green than compounds substituted with hydrogen. When used as a light emitting auxiliary layer, the efficiency was similar or slightly increased, it was confirmed that the improved results in terms of driving voltage and lifetime.

As described above, when a compound having a different bonding position of a carbazole and a linking group and a bonding position of a linking group and an amine group is applied to the hole transport layer and / or the light emitting auxiliary layer, the performance of the device is different. It can be seen that the bonding position of the group and the amine group acts as a major factor in the device performance.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is filed with the Korean Patent Application No. Priority is claimed under section (a) (35 USC § 119 (a)), all of which is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims

Compound represented by the following formula (1):

<Formula 1>

In Formula 1, L is
or
Where (* denotes the position to which the amine group in the formula 1 is bonded with nitrogen),

Ar 1 to Ar 3 are each independently of the other C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof.

a, b and m are each an integer of 0 to 4, n is an integer of 0 to 3,

R 1 to R 4 are each independently of i) deuterium; Tritium; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; -L'-N (R a ) (R b ); And combinations thereof, or ii) at least one pair of adjacent groups combine with each other to form at least one ring, wherein R 1 to R 4 , which do not form a ring, are each defined in i). Same as

L 'is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P, wherein R a and R b are each independently C 6 -C 60 aryl group; Fluorenyl group; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P,

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group each of deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Of C 6 -C 20 Aryl group; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And C 8 -C 20 arylalkenyl group; may be optionally substituted with one or more substituents selected from the group consisting of.
The method of claim 1,

wherein a and b are both O or R 3 and R 4 are each independently selected from the following structures:

.
The method of claim 1,

At least one of R 1 and R 2 is a compound characterized in that adjacent groups are bonded to each other to form a ring.
The method of claim 3, wherein

Compounds characterized in that represented by one of the following formula:

In Formulas 2 to 10, Ar 1 to Ar 3 , L, R 1 , R 2 , m and n are the same as defined in claim 1.
The method of claim 1,

Ar 1 is a compound which is selected from the following structures:

,
,

In the above structure, X is O, S or C (R ') (R "), wherein R' and R" are independently of each other, hydrogen; heavy hydrogen; Tritium; Aryl group of C 6 -C 20 ; An alkyl group of C 1 -C 20 ; And an alkenyl group of C 2 -C 20 ; and R ′ and R ″ may be bonded to each other to form a spiro compound together with carbon to which they are bonded,

o is an integer from 0 to 4, p is an integer from 0 to 3, R 5 and R 6 are independently from each other, i) deuterium; Tritium; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof, or ii) at least one pair of adjacent groups combine with each other to form at least one ring, provided that R 5 and R 6 , which do not form a ring, are defined in i) Same as
The method of claim 5,

Ar 1 is
,
or
ego,

Formula 1 is a compound characterized in that represented by one of the following formula 11 to formula 20:

In Chemical Formulas 11 to 20, Ar 2 , Ar 3 , L, R 1 , R 2 , m and n are the same as defined in claim 1, and X, R 5 , R 6 , o and p are 5. Same as defined in
The method of claim 1,

Ar 2 and Ar 3 are independently of each other selected from the following structures:

.
The method of claim 1,

Compounds characterized in that one of the following compounds:

.
A first electrode; Second electrode; And an organic material layer formed between the first electrode and the second electrode.

The organic material device, characterized in that the organic layer contains the compound of claim 1.
The method of claim 9,

The compound is contained in 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,

The compound is an organic electric device, characterized in that one kind or a mixture of two or more.
The method of claim 9,

And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
The method of claim 9,

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 comprising the organic electroluminescent element of claim 9; And

And a controller for driving the display device.
The method of claim 13,

The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.