WO2018016786A1 - Compound for organic electronic device, organic electronic device using same, and electronic apparatus thereof - Google Patents

Abstract

The present invention provides: a compound capable of implementing high luminous efficiency, a low driving voltage and improved lifespan of a device; an organic electronic device using the same; and an electronic apparatus thereof.

Description

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

The present embodiments relate to a compound for an organic electric element, an organic electric element 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.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like according to their functions.

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 efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases. The lifespan tends to increase. However, simply improving the organic material layer does not maximize the efficiency. Because of the optimal combination of energy level, triplet excitation energy value (hereinafter denoted as T1), and material intrinsic properties (mobility, interfacial properties, etc.) between organic layers, long life and high efficiency can be achieved simultaneously. Because it can.

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

In general, in the organic electroluminescent device, 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 of electrons and holes.

However, the materials used in the hole transport layer have a low TMO value because they have a low HOMO 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. However, this cannot be achieved simply by the structural properties of the core of the light emitting auxiliary layer material, but only when the properties of the core and the sub-substituent of the material are combined. 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.

In other words, in order to fully exhibit the excellent characteristics of the organic electric device, materials forming 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.

The present invention provides a compound capable of improving the luminous efficiency and lifespan while lowering the driving voltage of the device by introducing a specific substituent and limiting specific substitution positions of the three amine groups, and providing an organic electric device using the same and an electronic device thereof. The purpose.

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 the inventive compound, not only can the drive voltage of the device be lowered, but also the luminous efficiency and lifetime of the device can be greatly improved.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

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 addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (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".

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 "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

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 "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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 terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, fluorene group, spirofluorene group, spirobifluorene group.

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

Also, when prefixes are named consecutively, it means that the 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.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

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

"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.

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

Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, 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 substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but 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 formula.

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. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

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.

The compound according to the present invention applied to the organic material layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improvement layer of the light emitting layer 150 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, 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.

Therefore, in the present invention, by forming a light emitting layer using the compound represented by the formula (1), by optimizing the energy level (level) and T1 value between each organic layer, the intrinsic properties (mobility, interfacial characteristics, etc.) of the organic layer Can improve the service life and efficiency at the same time.

The organic electric device according to the embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or 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 have been proposed and patented for the white organic electric element mainly used as a backlight device. 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 device for monochrome or white illumination.

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

In the above formula (1),

1) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ are the same as or different from each other independently, C ₆ ~ C ₆₀ An aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; C ₆ -C ₆₀ arylene group; fluorenylene group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; and a hetero ring group of C ₂ ~ C ₆₀ ; wherein R _a and R _b are independently of each other C ₆ ~ C ₆₀ Aryl group; fluorenyl group; C ₃ ~ C ₆₀ alicyclic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring group; and O, N, S, Si and P containing at least one heteroatom ₂ or a heterocyclic group of C _60; selected from the group consisting of a) Ar ^1, Ar ^2, Ar ^3, Ar ^4, at least one of Ar ⁵ is substituted by the formula (1-1),

2) n, m, p are integers from 0 to 4, o is an integer from 0 to 3, when m, n, o, p is 1 or more, R ¹ , R ² , R ³ , R ⁴ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C for ₂ ~ C ₂₀ alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); selected from the group consisting of or neighboring a plurality of R ¹ , or a plurality of R ² , or a plurality of R ³ , or a plurality of R ⁴ are bonded to each other To form an aromatic or heteroaromatic ring,

3) X is selected from either O or S,

4) L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, aryloxy group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group each of deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R _a ) (R _b ), wherein L ', R _a , R _b are the same as defined above for L', R _a , R _b ; 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 ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl groups; 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 it may be further substituted with one or more substituents selected from the group consisting of C ₈ -C ₂₀ arylalkenyl group, and these substituents may be bonded to each other to form a ring, wherein the 'ring' is an aliphatic having 3 to 20 carbon atoms It refers to a fused ring consisting of a ring or an aromatic ring having 6 to 20 carbon atoms or a hetero ring having 2 to 20 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring.

Here, in the case of the aryl group, the carbon number may be 6 to 60, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, the carbon number is 2 to 60, preferably 2 carbon atoms. ˜30, more preferably a hetero ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the carbon number is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably It may be an alkyl group of 1 to 10.

In the case of the aforementioned aryl group or arylene group, specifically, the aryl group or arylene group is independently of each other a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group or phenylene group, biphenylene group, terphenylene group, naphthyl Lene group, phenanthryl group, pyrene or triphenylene and the like.

More specifically, the compound represented by Formula (1) may be any one of the following compounds, but is not limited to the following compounds.

Formula (1) may be represented by one of the following formulas (2) to (5).

In the above formulas (2) to (5),

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , n, m, p, o, R ¹ , R ² , R ³ , R ⁴ , X, L are Ar ¹ , defined in Formula (1) above Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , n, m, p, o, R ¹ , R ² , R ³ , R ⁴ , X, L are the same.

More specifically, the compound represented by Formula (1) may be any one of the following compounds, but is not limited to the following compounds.

As another embodiment, the present invention provides a compound for an organic electric device represented by the 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 Formula (1), and the compound represented by Formula (1) may be a hole injection of an organic material layer. It may be contained in at least one of a layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron auxiliary layer, an electron transport layer and an electron injection layer. In particular, the compound represented by the formula (1) may be included in the hole transport layer or the light emitting auxiliary layer.

That is, the compound represented by the formula (1) may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron auxiliary layer, an electron transport layer or an electron injection layer. In particular, the compound represented by the formula (1) can be used as a material of the light emitting layer. Specifically, to provide an organic electroluminescent device comprising one of the compounds represented by the formula (1) in the organic material layer, more specifically, the compound represented by the individual formulas (P-1 to P-68) in the organic material layer It provides an organic electric element comprising one of.

In another embodiment, the compound is alone in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron auxiliary layer, the electron transport layer and the electron injection layer of the organic material layer. It is contained, or the compound is contained in a combination of two or more different from each other, or the compound is provided with an organic compound, characterized in that the compound contained in a combination of two or more. In other words, each of the layers may include a compound corresponding to formula (1) alone, may include a mixture of two or more compounds of formula (1), the compound of claims 1 to 3, and Mixtures with compounds not applicable may be included. Herein, the compound not corresponding to the present invention may be a single compound or two or more compounds. In this case, when the compound is contained in a combination of two or more kinds of other compounds, the other compound may be a known compound of each organic material layer, or a compound to be developed in the future. In this case, the compound contained in the organic material layer may be made of only the same kind of compound, but may be a mixture of two or more kinds of the compound represented by the formula (1).

In another embodiment of the present invention, further comprising 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 device.

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

Synthesis Example

Compounds represented by the formula (1) according to the present invention (final product) is prepared by reacting Sub 1 or Sub 2 Sub 3 as shown in Scheme 1, but is not limited thereto.

I. Synthesis of Sub 1

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

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

Sub 1- 1 Synthesis Example

(1) Sub 1-I-1

After starting diphenylamine (50 g, 295.46 mmol) was dissolved in toluene (985 ml) in a round bottom flask, 1-bromo-3-chlorobenzene (68 g, 354.54 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.86 mmol), 50% P ( t -Bu) ₃ (7.1 ml, 17.72 mmol), NaO t -Bu (85.3 g, 886.36 mmol) was 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 Sub1-I-1 74.5 g (yield: 90%).

(2) Sub 1-II- 1 Synthesis

Sub-I-1 (75 g, 268.08 mmol), aniline (37.5 g, 402.11 mmol), Pd ₂ (dba) ₃ (7.4 g, 8.04 mmol), 50% P ( t -Bu) ₃ (6.5 ml, 16.08 mmol), NaO t -Bu (77.35 g, 804.23 mmol) was added to toluene (900 mL) and stirred at 130 ° C. 77.6 g (yield: 77.6%) of product Sub 1-II-1 was obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 1 Synthesis

Sub-II-1 (10 g, 29.72 mmol), 1-bromo-3-chlorobenzene (5.7 g, 29.72 mmol), Pd ₂ (dba) ₃ (1 g, 0.9 mmol), 50% P ( t -Bu) ₃ (0.8 ml, 0.9 mmol), NaO t -Bu (8.6 g, 89.17 mmol) was added to toluene (100 mL) and stirred at 130 ° C. 12 g (yield: 90.3%) of product Sub 1-1 was obtained through the Sub1-I-1 synthesis method.

2.Sub 1- 7 Synthesis Example

(1) Sub 1-I-7

Starting materials N-phenyldibenzo [b, d] thiophen-4-amine (50 g, 181.57 mmol), 1-bromo-3-chlorobenzene (34.7 g, 181.57 mmol), Pd ₂ (dba) ₃ (5 g, 5.47 mmol), 50% P ( t -Bu) ₃ (4.4 ml, 10.89 mmol), NaO t -Bu (52.4 g, 544.74 mmol) was added to toluene (600 mL) and stirred at 80 ° C. 49 g (yield: 70.3%) of product Sub 1-I-7 was obtained through the Sub1-I-1 synthesis method.

(2) Sub 1-II- 7 synthetic

Sub-I-1 (40 g, 103.89 mmol), 4- (4,6-diphenylpyrimidin-2-yl) aniline (33.6 g, 103.89 mmol), Pd ₂ (dba) ₃ (2.85 g, 3.11 mmol), 50 % P ( t -Bu) ₃ (2.5 ml, 6.23 mmol), NaO t -Bu (30 g, 311.68 mmol) was added to toluene (350 mL) and stirred at 130 ° C. 54 g (yield: 77.2%) of product Sub 1-II-7 was obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 7 synthetic

Sub-II-7 (10 g, 14.86 mmol), 1-bromo-3-chlorobenzene (2.84 g, 14.86 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (4.28 g, 44.5 mmol) was added to toluene (100 mL) and stirred at 130 ° C. The Sub1-I-1 synthesis gave 8 g (yield: 68.7%) of product Sub 1-7.

3.Sub 1- 10 Synthesis Example

(1) Sub 1-I-10

Starting materials diphenylamine (50 g, 295.46 mmol), 1-bromo-3-chloro-5-methylbenzene (70.6 g, 295.46 mmol), Pd ₂ (dba) ₃ (8.1 g, 8.86 mmol), 50% P ( t -Bu) ₃ (7.2 ml, 17.72 mmol), NaO t -Bu (85.2 g, 886.36 mmol) was added to toluene (1000 mL) and stirred at 80 ° C. 70 g (yield: 80.6%) of the product Sub 1-I-10 was obtained through the Sub1-I-1 synthesis method.

(2) Sub 1-II- 10 synthetic

Sub-I-1 (50 g, 208.51 mmol), aniline (19.4 g, 208.51 mmol), Pd ₂ (dba) ₃ (5.7 g, 6.26 mmol), 50% P ( t -Bu) ₃ (5 ml, 12.5 mmol), NaO t -Bu (60.1 g, 625.5 mmol) was added to toluene (700 mL) and stirred at 130 ° C. 64 g (yield: 87.6%) of the product Sub 1-II-10 was obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 10 synthetic

Sub-II-7 (10 g, 28.5 mmol), 1-bromo-3-chloro-5-methylbenzene (5.9 g, 28.5 mmol), Pd ₂ (dba) ₃ (0.78 g, 0.86 mmol), 50% P ( t- Bu) ₃ (0.7 ml, 1.7 mmol), NaO t -Bu (8.2 g, 85.59 mmol) was added to toluene (100 mL) and stirred at 130 ° C. The Sub1-I-1 synthesis gave 10 g (yield: 73.8%) of product Sub 1-10.

4.Sub 1- 19 Synthesis Example

(1) Sub 1-I-19

Starting materials N-phenyldibenzo [b, d] furan-2-amine (50 g, 192.8 mmol), 1-bromo-3-chlorobenzene (40 g, 192.8 mmol), Pd ₂ (dba) ₃ (5.3 g, 5.78 mmol), 50% P ( t -Bu) ₃ (4.6 ml, 11.6 mmol), NaO t -Bu (55.6 g, 578.45 mmol) was added to toluene (650 mL) and stirred at 80 ° C. 66 g (yield: 92.5%) of product Sub 1-I-19 was obtained through the Sub1-I-1 synthesis method.

(2) Sub 1-II- 19 synthetic

Sub-I-1 (60 g, 162.2 mmol), aniline (15.6 g, 162.2 mmol), Pd ₂ (dba) ₃ (4.5 g, 4.86 mmol), 50% P ( t -Bu) ₃ (4 ml, 9.73 mmol), NaO t -Bu (46.8 g, 486.4 mmol) was added to toluene (550 mL) and stirred at 130 ° C. 58 g (yield: 83.8%) of the product Sub 1-II-19 were obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 19 synthetic

Sub-II-7 (15 g, 35.2 mmol), 1-bromo-3-chlorobenzene (6.7 g, 35.2 mmol), Pd ₂ (dba) ₃ (0.9 g, 1.1 mmol), 50% P ( t -Bu) ₃ (0.8 ml, 2.1 mmol), NaO t -Bu (10.1 g, 105.5 mmol) was added to toluene (110 mL) and stirred at 130 ° C. 16 g (yield: 84.7%) of product Sub 1-19 was obtained through the Sub1-I-1 synthesis method.

5.Sub 1- 20 Synthesis Example

(1) Sub 1-I-20

Starting materials diphenylamine (50 g, 295.46 mmol), 1-bromo-3-chlorobenzene (68 g, 354.54 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.86 mmol), 50% P ( t -Bu) ₃ (7.1 ml, 17.72 mmol), NaO t -Bu (85.3 g, 886.36 mmol) was added to toluene (1000 mL) and stirred at 80 ° C. The Sub1-I-1 synthesis gave 74.5 g (yield: 90%) of product Sub 1-20.

(2) Sub 1-II- 20 synthetic

Sub-I-20 (50 g, 178.71 mmol), dibenzo [b, d] thiophen-2-amine (35.6 g, 178.71 mmol), Pd ₂ (dba) ₃ (4.9 g, 5.36 mmol), 50% P ( t -Bu) ₃ (4.4 ml, 10.72 mmol), NaO t -Bu (51.5 g, 536.15 mmol) was added to toluene (600 mL) and stirred at 130 ° C. 71 g (yield: 89.9%) of the product Sub 1-II-20 was obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 20 synthetic

Sub-II-20 (15 g, 33.9 mmol), 1-bromo-3-chlorobenzene (6.5 g, 33.9 mmol), Pd ₂ (dba) ₃ (0.9 g, 1.01 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 2.04 mmol), NaO t -Bu (9.8 g, 101.8 mmol) was added to toluene (110 mL) and stirred at 130 ° C. The Sub1-I-1 synthesis gave 18 g (yield: 95.9%) of product Sub 1-20.

6.Sub 1- 33 Synthesis Example

(1) Sub 1-I-33

Di ([1,1'-biphenyl] -3-yl) amine (100 g, 311.1 mmol), 1-bromo-3-chlorobenzene (59.5 g, 311.1 mmol), Pd ₂ (dba) ₃ (8.55 g, 9.33 mmol), 50% P ( t -Bu) ₃ (7.4 ml, 18.6 mmol), NaO t -Bu (89.8 g, 933.3 mmol) was added to toluene (1000 mL) and stirred at 80 ° C. 121 g (yield: 90%) of product Sub 1-20 was obtained through the Sub1-I-1 synthesis method.

(2) Sub1 -II- 33 synthetic

Sub-I-33 (70 g, 162.4 mmol), dibenzo [b, d] thiophen-2-amine (32.3 g, 162.4 mmol), Pd ₂ (dba) ₃ (4.5 g, 4.87 mmol), 50% P ( t- Bu) ₃ (4 ml, 9.74 mmol), NaO t -Bu (46.8 g, 487.23 mmol) was added to toluene (900 mL) and stirred at 130 ° C. 80 g (yield: 82.8%) of the product Sub 1-II-33 was obtained through the Sub1-I-1 synthesis method.

(3) Sub1 - 33 synthetic

Sub-II-20 (15 g, 25.2 mmol), 1-bromo-3-chlorobenzene (4.81 g, 25.2 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.76 mmol), 50% P ( t -Bu) ₃ (0.6 ml, 1.51 mmol), NaO t -Bu (7 g, 75.6 mmol) was added to toluene (100 mL) and stirred at 130 ° C. 17 g (yield: 78.7%) of product Sub 1-33 was obtained through the Sub1-I-1 synthesis method.

7.Sub 1- 48 Synthesis Example

(1) Sub 1-I-48

Starting materials diphenylamine (50 g, 295.46 mmol), 1-bromo-3-chlorobenzene (68 g, 354.54 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.86 mmol), 50% P ( t -Bu) ₃ (7.1 ml, 17.72 mmol), NaO t -Bu (85.3 g, 886.36 mmol) was added to toluene (1000 mL) and stirred at 80 ° C. The Sub1-I-1 synthesis gave 74.5 g (yield: 90%) of product Sub 1-20.

(2) Sub 1-II- 48 synthetic

Sub-I-20 (50 g, 178.71 mmol), 4- (dibenzo [b, d] furan-2-yl) aniline (46.3 g, 178.71 mmol), Pd ₂ (dba) ₃ (4.9 g, 5.36 mmol) , 50% P ( t -Bu) ₃ (4.4 ml, 10.72 mmol), NaO t -Bu (51.5 g, 536.15 mmol) was added to toluene (600 mL) and stirred at 130 ° C. 55 g (yield: 61.2%) of product Sub 1-II-48 was obtained through the Sub1-I-1 synthesis method.

(3) Sub 1- 48 synthetic

Sub-II-48 (10 g, 19.9 mmol), 1-bromo-3-chlorobenzene (3.8 g, 19.9 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.59 mmol), 50% P ( t -Bu) ₃ (0.5 ml, 1.2 mmol), NaO t -Bu (5.7 g, 59.7 mmol) was added to toluene (100 mL) and stirred at 130 ° C. The Sub1-I-1 synthesis gave 11 g (yield: 91%) of the product Sub 1-48.

The compound belonging to Sub 1 may be, but is not limited to, the following compounds. Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1.

II. Synthesis of Sub 2

Sub 2 of Scheme 7 may be synthesized by the reaction route of Scheme 10, but is not limited thereto.

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

Sub 2-1 Synthesis Example

To the starting material 2-bromodibenzo [b, d] thiophene (38.11 g, 144.82 mmol) aniline (14.84 g, 159.30 mmol), Pd ₂ (dba) ₃ (3.98 g, 4.34 mmol), 50% P ( t -Bu ) ₃ (5.6 ml, 11.59 mmol), NaO t -Bu (41.76 g, 434.47 mmol), toluene (760 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 recrystallization to obtain 30.7 g (yield: 77%) of the product Sub2-1.

2.Sub 2-29 Synthesis Example

Aniline (5.8 g, 61.8 mmol), Pd ₂ (dba) ₃ (1.7 g, 1.85 mmol), 50% in starting material 4- (4-bromophenyl) dibenzo [b, d] furan (20 g, 61.8 mmol) P ( t -Bu) ₃ (1.5 ml, 3.71 mmol), NaO t -Bu (17.8 g, 185.6 mmol), toluene (200 ml) were added and 17 g of product Sub2-29 was synthesized using the above Sub 2-1 synthesis. (Yield 82%) was obtained.

3.Sub 2-31 Synthesis Example

After starting bromobenzene (40.68 g, 259.09 mmol) was dissolved in toluene (1360 ml) in a round bottom flask, aniline (26.54 g, 285.00 mmol), Pd ₂ (dba) ₃ (7.12 g, 7.77 mmol), 50% P ( t -Bu) ₃ (10.1 ml, 20.73 mmol), NaO t -Bu (74.70 g, 777.28 mmol) were added and 32.88 g (Yield: 75%) of Sub2-31 was obtained using the Sub 2-1 synthesis method. Got it.

4.Sub 2-34 Synthesis Example

In the starting material 4-bromo-1,1'-biphenyl (23.65 g, 101.46 mmol) aniline (10.39 g, 111.60 mmol), Pd ₂ (dba) ₃ (2.79 g, 3.04 mmol), 50% P ( t- Bu) ₃ (4.0 ml, 8.12 mmol), NaO t -Bu (29.25 g, 304.38 mmol), toluene (710 ml) were added and 20.66 g of product Sub2-34 was obtained using the Sub 2-1 synthesis method (yield: 83 %) Was obtained.

5.Sub 2-35 Synthesis Example

To starting material 2- (4-bromophenyl) pyridine (10.53 g, 44.98 mmol) aniline (4.61 g, 49.48 mmol), Pd ₂ (dba) ₃ (1.24 g, 1.35 mmol), 50% P ( t -Bu) ₃ (1.8 ml, 3.60 mmol), NaO t -Bu (12.97 g, 134.95 mmol), toluene (315 ml) were added and the product 787 g (yield: 71%) was obtained using the Sub 2-1 synthesis method.

Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.

III. Product Synthesis

Sub 1 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 2 (1 equiv), Pd ₂ (dba) ₃ (0.03 equiv), (t-Bu) 3 P (0.06 equiv), NaOt-Bu (3 equiv) were stirred at 135 ° C. for 3 hours. 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 a final product.

1.P-1 Synthesis Example

Sub 1-1 (20 g, 44.7 mmol) obtained in the above synthesis was dissolved in toluene (150 ml) in a round bottom flask, and then Sub 2-1 (12.3 g, 44.7 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol), 50% P ( t -Bu) ₃ (1 ml, 2.68 mmol), NaO t -Bu (13 g, 134.2 mmol) was added and stirred at 135 ° C. After completion of the reaction, the mixture was extracted with toluene and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain 22 g (yield: 71.7%) of product P-1.

2. P-12 Synthesis Example

Sub 1-1 (20 g, 44.7 mmol), Sub 2-8 (19 g, 44.7 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol) obtained in the above synthesis, 50% P ( t -Bu) ₃ (1 ml, 2.68 mmol), NaO t -Bu (13 g, 134.2 mmol) was added to toluene (150 ml) and stirred at 135 ° C. 35 g (yield: 93.6%) of product P-12 was obtained using the P-1 separation method.

3.P-25 Synthesis Example

Sub 1-20 (10 g, 18 mmol), Sub 2-31 (3.1 g, 18 mmol) obtained in the above synthesis, Pd ₂ (dba) ₃ (0.5 g, 0.54 mmol), 50% P ( t -Bu) ₃ (0.42 ml, 1.1 mmol), NaO t -Bu (5.2 g, 54.4 mmol) was added to toluene (100 ml) and stirred at 135 ° C. Using the P-1 separation method, 10 g (yield: 80.6%) of product P-25 was obtained.

4.P-36 Synthesis Example

Sub 1-33 (10 g, 14 mmol), Sub 2-30 (5.4 g, 14 mmol) obtained in the above synthesis, Pd ₂ (dba) ₃ (0.4 g, 0.42 mmol), 50% P ( t -Bu) ₃ (0.32 ml, 0.83 mmol), NaO t -Bu (4 g, 41.9 mmol) was added to toluene (80 ml) and stirred at 135 ° C. 13 g (yield: 87.4%) of product P-36 was obtained using the P-1 separation method.

5. P-39 Synthesis Example

Sub 1-36 (15 g, 23.8 mmol), Sub 2-31 (4 g, 23.8 mmol), Pd ₂ (dba) ₃ (0.65 g, 0.71 mmol) obtained in the above synthesis, 50% P ( t -Bu) ₃ (0.58 ml, 1.4 mmol), NaO t -Bu (6.9 g, 71.5 mmol) was added to toluene (120 ml) and stirred at 135 ° C. 13 g (yield: 71.6%) of product P-39 was obtained using the above P-1 separation method.

6.P-64 Synthesis Example

Sub 1-54 (15 g, 19.1 mmol), Sub 2-35 (4.7 g, 19.1 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.57 mmol) obtained in the above synthesis, 50% P ( t -Bu) ₃ (0.46 ml, 1.2 mmol), NaO t -Bu (5.5 g, 57.5 mmol) was added to toluene (110 ml) and stirred at 135 ° C. 15 g (yield: 78.9%) of product P-64 was obtained using the P-1 separation method.

On the other hand, FD-MS values of the compounds P-1 to P-68 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

Manufacturing Evaluation of Organic Electrical Device

Example 1 Fabrication and Test of Red Organic Light-Emitting Device (Emission Layer)

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, N, N'-Bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as NPB) is 60 nm thick. Vacuum deposition was performed to form a hole transport layer. Subsequently, the inventive compound represented by the formula (1) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. After the emission auxiliary layer was formed, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host on the emission auxiliary layer, and as a dopant, (piq) ₂ Ir (acac) [bis- ( A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping 1-phenylisoquinolyl) iridium (III) acetylacetonate] at a weight of 95: 5. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement results were obtained at a luminance of 2500 cd / m2. The T95 life was measured using a life measurement instrument manufactured by McScience. The following table shows the results of device fabrication and evaluation.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emitting auxiliary layer was not used.

[Comparative Example 2 to Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compounds A to D were used as the light emitting auxiliary layer material.

As can be seen from the results of Table 4, when the red organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as a light emitting auxiliary layer material, the light emitting auxiliary layer was not used or Comparative Compounds A to D were used. It can be seen that not only can the driving voltage of the organic electroluminescent device be lowered than the comparative example used, but also the light emitting efficiency and life can be significantly improved.

In other words, the results of Comparative Examples 2 to 5 using Comparative Compounds A to D were superior to Comparative Example 1 without using the light emitting auxiliary layer, and two or more phenyls substituted at the meta position must be substituted than the Comparative Compounds. Examples 1 to 64 of the compound of the present invention in which one or more dibenzothiophen or dibenzofuran derivative compounds were substituted showed the best results.

Comparing in detail, the results of Comparative Compounds B, C, and D, which were substituted with a specific substituent called dibenzothiophen, were superior to those of Comparative Compound A, where the substituent was a simple aryl group, and all of them were meta-substituted compared to Comparative Compounds B and C where phenyl was substituted at the para position. The comparative compound D having one substituted phenyl was better, and more than two phenyl substituted at the meta position must be substituted, and the compound of the present invention in which at least one dibenzothiophen or dibenzofuran derivative compound was substituted was the driving voltage and efficiency. And it can be seen that it shows a remarkably excellent result in terms of life. The presence of two phenyls substituted at the meta position results in shorter conjugation lengths of the compounds than those of the comparative compounds, deep HOMO energy levels, and high T1 values, thereby allowing holes to be transported to the light emitting layer smoothly. It is believed that the efficiency and lifespan are improved by improving the ability to block. In addition, as the specific substituents such as dibenzothiophen or dibenzofuran are substituted, the properties of compounds such as hole characteristics, light efficiency characteristics, energy levels (LUMO, HOMO levels), hole injection & mobility characteristics, and electron blocking characteristics are improved, thereby improving device performance during device deposition. It can be seen that these different results are obtained by acting as a major factor in (especially, improving efficiency).

Therefore, this suggests that the phenyl compound substituted by meta position must be substituted at least two, and the compound of the present invention in which at least one dibenzothiophen or dibenzofuran derivative compound is substituted may have significantly different chemical and physical properties from the existing compounds.

Example 2 Fabrication and Test of Red Organic Light-Emitting Device (Hole Transport Layer)

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, the inventive compound represented by the formula (2) was vacuum deposited to a thickness of 60 nm as a hole transport layer material to form a hole transport layer. CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host on the hole transport layer, and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate as a dopant ] Was deposited to a weight of 95: 5 to deposit a 30 nm thick light emitting layer. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement results were obtained at a luminance of 2500 cd / m2. The T95 life was measured using a life measurement instrument manufactured by McScience. The following table shows the results of device fabrication and evaluation.

Comparative Example 6

N, N'-Bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as NPB) as the hole transport layer material Except for the organic electroluminescent device was manufactured in the same manner as in Example 2.

[Comparative Example 7 to Comparative Example 10]

An organic electroluminescent device was manufactured in the same manner as in Example 2, except that Comparative Compounds A to D were used as the hole transport layer material.

As can be seen from the results in Table 5, when the red organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as a hole transporting layer material, it was compared to the comparative examples using NPB or Comparative Compounds A to D. It can be seen that not only can the driving voltage of the organic electroluminescent device be lowered, but the light emitting efficiency and lifetime can be improved.

As described in Table 4, it is necessary that two or more phenyls substituted in the meta position are substituted, and the compound of the present invention in which one or more dibenzothiophen or dibenzofuran derivative compounds are substituted may have significantly different chemical and physical properties from the existing compounds. This suggests that different device results can be derived.

The present invention has been described above by way of example, and those skilled in the art will appreciate that various modifications may be made 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 claims priority under Patent Application No. 10-2016-0093576, filed in South Korea on July 22, 2016, pursuant to Section 119 (a) (35 USC § 119 (a)). All content 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 (10)

The compound represented by following formula (1).

In the above formula (1), 1) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ are the same as or different from each other independently, C ₆ ~ C ₆₀ An aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; C ₆ -C ₆₀ arylene group; fluorenylene group; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; and a hetero ring group of C ₂ ~ C ₆₀ ; wherein R _a and R _b are independently of each other C ₆ ~ C ₆₀ Aryl group; fluorenyl group; C ₃ ~ C ₆₀ alicyclic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring group; and O, N, S, Si and P containing at least one heteroatom ₂ or a heterocyclic group of C _60; selected from the group consisting of a) Ar ^1, Ar ^2, Ar ^3, Ar ^4, at least one of Ar ⁵ is substituted by the formula (1-1), 2) n, m, p are integers from 0 to 4, o is an integer from 0 to 3, when m, n, o, p is 1 or more, R ¹ , R ² , R ³ , R ⁴ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C for ₂ ~ C ₂₀ alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); selected from the group consisting of or neighboring a plurality of R ¹ , or a plurality of R ² , or a plurality of R ³ , or a plurality of R ⁴ are bonded to each other To form an aromatic or heteroaromatic ring, 3) X is selected from either O or S, 4) L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P. The aryl group, fluorenyl group, heterocyclic group, fused ring group, aryloxy group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group each of deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R _a ) (R _b ), wherein L ', R _a , R _b are the same as defined above for L', R _a , R _b ; 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 ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl groups; 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 it may be further substituted with one or more substituents selected from the group consisting of C ₈ -C ₂₀ arylalkenyl group, and these substituents may be bonded to each other to form a ring, wherein the 'ring' is an aliphatic having 3 to 20 carbon atoms It refers to a fused ring consisting of a ring or an aromatic ring having 6 to 20 carbon atoms or a hetero ring having 2 to 20 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring. The method of claim 1, A compound represented by the formula (1) is represented by any one of the following formulas (2) to (5).

In the above formulas (2) to (5), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , n, m, p, o, R ¹ , R ² , R ³ , R ⁴ , X, L are Ar ¹ , defined in Formula (1) above Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , n, m, p, o, R ¹ , R ² , R ³ , R ⁴ , X, L are the same. The method of claim 1, The compound represented by the formula (1) is any one of the compounds represented by the following formula.

A first electrode; Second electrode; And An organic electronic device comprising: an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains a compound according to any one of claims 1 to 3. The method of claim 4, wherein The compound is contained in at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, and an electron auxiliary layer of the organic material layer, the compound comprises one or more compounds or two or more compounds as a component of the mixture An organic electric element, characterized in that. The method of claim 4, wherein The compound is an organic electric device, characterized in that used as a hole transport layer or a light emitting auxiliary layer. The method of claim 4, wherein And an optical efficiency improvement 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 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. Claim 4 display device comprising the organic electroluminescent element; And And a controller for driving the display device. The method of claim 9, The organic electronic device is an electronic device, characterized in that one of an organic light emitting device, an organic solar cell, an organic photoconductor, an organic transistor, and a device for monochrome or white illumination.

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