WO2017142229A1 - Compound for organic electric element, organic electric element using same, and electronic device comprising same - Google Patents

Abstract

The present invention provides: a compound capable of achieving high luminous efficiency, a low driving voltage, and an improved lifetime of an element; an organic electric element using the same; and an electronic device comprising the same.

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 a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also 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.

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 demanded, and in particular, the development of the material of the light emitting layer, especially the host material of the light emitting 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 of the formula

The present invention also provides an organic electric device using the compound having the above formula and a terminal including the organic electric device.

The compound of the present invention may play various roles in the organic electric device and the terminal, and when applied to the organic electric device and the terminal, it is possible to lower the driving voltage of the device, improve light efficiency and lifespan, and stability of the device.

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, the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layer, and thus the life of the organic electric device. And efficiency can be improved at the same time.

The organic light emitting 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 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 light emitting diode (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. Compound according to an aspect of the present invention is represented by the following formula (1).

    Formula (1)

1) X is ^one of NR ¹ , S, O, CR'R ”,

2) n and m are 0 or 1, n + m is 1 or more,

(Where n and m are 0, A and B are single bonds to form pentagonal rings)

3) A and B are each independently a single bond, NR ¹ , S, O, CR'R ”,

4) Z ¹ to Z ¹² are each independently CR ² , N and at least one is N,

5) R ¹ and R ² are independently of each other 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 );

(Wherein L ′ is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; and C ₂ ~ C ₆₀ heterocyclic group; selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Selected from the group consisting of a fused ring group of an aromatic ring of C and a C ₂ ~ C ₆₀ hetero ring group containing at least one hetero atom of O, N, S, Si and P), or adjacent R ¹ , Adjacent R ² may combine with each other to form a ring,

When at least two of Z ¹ to Z ¹² are CR ² , each CR ² may be independently of each other, and each CR ² may be the same or different.

6) R ′ and R ″ are each independently hydrogen, a C ₁ to C ₅₀ alkyl group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of, can be combined with each other to form a spiro compound.

When the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, arylene group, fluorenylene group, each of these are 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; 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 when these substituents are adjacent to each other they may combine with each other to form a 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 Or a phenanthrene group or 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 (3).

    Formula (2) Formula (3)

Z ¹ to Z ¹² , X, A, and B are the same as Z ¹ to Z ¹² , X, A, and B defined in Chemical Formula (1).

Formula (1) may be represented by one of the following formula (4) to formula (11).

Z ¹ to Z ¹² , R ¹ , R ² , R ′, R ″, A, and B are Z ¹ to Z ¹² , R ¹ , R ¹ , R ² , R ′, R ″, and A as defined in Formula (1). , Like B

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to 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 the compound represented by Chemical Formula 1 may be a hole injection layer or a hole transport layer of the organic material layer. The light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may be contained in at least one layer. In particular, the compound represented by Formula 1 may be included in the hole transport layer or the light emitting auxiliary 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, a light emitting layer, an electron transport auxiliary layer, an electron transport layer or an electron injection layer. In particular, the compound represented by Formula 1 may 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, It provides an organic electroluminescent device comprising a compound represented by the individual formulas (1-1 to 9-18) in the organic layer.

In another embodiment, the compound is in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport auxiliary layer, the electron transport layer and the electron injection layer of the organic material layer. Provided is an organic electric device characterized in that it is contained alone, or the compound is contained in two or more kinds of combinations different from each other, or the compound is contained in two or more kinds of combinations with other compounds. In other words, each of the layers may include a compound corresponding to Formula 1 alone, and may include a mixture of two or more compounds of Formula 1, the compounds of claims 1 to 4, and compounds not corresponding to the present invention. And mixtures thereof. 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 only of the same kind of compound, but may be a mixture of two or more kinds of the compound represented by the formula (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 compound represented by the formula (1) 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.

 Synthesis Example

Compounds represented by the formula (1) according to the present invention (final product) Sub 1 is prepared by the method of (1) to (4) as shown in Scheme 1.

<Scheme 1>

Sub A Synthesis Example

Sub A of Scheme 1 may be synthesized by the reaction route of Schemes 2 to 5, but is not limited thereto.

1) Synthesis of Sub A (1)

Synthesis of Sub A (1) -3

Sub A (1) -1, Sub A (1) -2 K ₂ CO ₃ and Pd (PPh ₃ ) ₄ were dissolved in anhydrous THF and a small amount of water, and then refluxed at 80 ° C. for 12 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting organic was separated using a silicagel column to obtain the desired Sub A (1) -3.

Synthesis of Sub A (1) -4

Sub A (1) -3 and triphenylphosphine obtained were dissolved in o- dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was recrystallized from a silicagel column to obtain the desired Sub A (1) -4.

Synthesis of Sub A (1)

After Sub A (1) -4 was dissolved in toluene, Sub A (1) -5 was added and Pd ₂ (dba) ₃ , P (t-Bu) ₃ , NaO t -Bu, and toluene were respectively added. The mixture was stirred at reflux for 24 hours. 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 organic substance was purified by silicagel column and recrystallized to obtain Sub A (1).

2) Synthesis of Sub A (2)

Sub A (2) -1, Sub A (2) -2, NH ₃ , were reacted at room temperature for 10 minutes. After the reaction was completed, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organics were separated using a silicagel column to obtain the desired Sub A (2).

3) Synthesis of Sub A (3)

<Scheme 4>

Cs ₂ CO ₃ , Pd (OAc) ₂ , and PPh ₃ were added to Sub A (3) -1 and Sub A (3) -2 and dissolved in DMF, followed by reaction at 140 ° C. for 15 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, the organic layer was dried and concentrated, and the resultant organic material was separated using a silicagel column to obtain a desired Sub A (3).

4) Synthesis of Sub A (4)

Scheme 5

Synthesis of Sub A (4) -2

ET ₃ N, Pd (OAc) ₂ and PPH ₃ were added to Sub A (4) -1, dissolved in DMF and a small amount of water, and reacted at 130 ° C. for 22 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, the organic layer was dried and concentrated, and the resulting organic was separated using a silicagel column to obtain a desired Sub A (4) -2.

Synthesis of Sub A (4) -3

Sub A (4) -2 was dissolved in diethylether and AlCl ₃ was added slowly. It was stirred for 15 minutes, then cooled to 0 ° C. and lithium aluminum hydride (LAH) was added slowly. Thereafter, the mixture was stirred under reflux for 1 hour, and when the reaction was completed, the mixture was slowly cooled to room temperature, and EA was slowly added thereto until no bubble occurred. Then HCL was added and extracted with distillation and ethyl acetate. The organic layer was dried over MgSO ₄ , concentrated, and the resulting organic was separated using a silicagel column to obtain the desired Sub A (4) -3.

Synthesis of Sub A (4) -4

Sub A (4) -3 was dissolved in DMSO, and sodium tert-butoxide was added at room temperature, followed by stirring at 70 ° C. for 15 minutes. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added and stirred for 20 minutes. At this time, a solid was formed, which was filtered, and the obtained solid was recrystallized from methanol and acetone to obtain Sub A (4).

[Final product 1, 2 Synthesis Example: Path (1)]

Product 1 and 2 of Scheme 1 may be synthesized by the reaction route of Scheme 6, but is not limited thereto.

<Scheme 6>

Synthesis Example of 5-17

Synthesis of Sub 2-1

Sub A (1) -1 (46.6 g, 0.11 mol), Sub 1-1 (15.2 g, 0.13 mol), K ₂ CO ₃ (46.03 g, 0.33 mol), Pd (PPh ₃ ) ₄ (5.13 g, 4 mol%) was dissolved in anhydrous THF and a small amount of water and then refluxed at 80 ° C. for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ , concentrated, and the resultant organics were separated using a silicagel column. 40.5 g, 80%).

Synthesis of Sub 3-1

Sub 2-1 (40.5g, 0.09 mol) and triphenylphosphine (0.3 mol) were dissolved in o -dichlorobenzene and refluxed for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the concentrated product was purified by silicagel column and recrystallization to obtain the desired Sub 3-1 (30.2 g, 80%).

Synthesis of 5-17

Sub 3-1 (10.4g, 24mmol) was dissolved in toluene, then Sub 5-1 (3.8g, 20mmol) was added and Pd ₂ (dba) ₃ (0.5g, 0.6mmol), P (t-Bu) ₃ ( 0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (300 mL) were added, and the mixture was stirred under reflux for 24 hours at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 10.2 g (yield: 83%) of the final compound.

Synthesis Example of 2-18

Synthesis of Sub 2-2

Sub A (2) -1 (34.6g, 0.11 mol) and Sub 1-1 (15.2, 0.13 mol) were prepared using the same synthesis method as Sub 2-1 to Sub 2-2 (31.4 g, 80%). Got it.

Synthesis of Sub 3-2

Obtained Sub 2-2 (31.4g, 0.09 mol) to the desired Sub 3-2 (22.8g, 80%) by the same synthesis method as Sub 3-1 Sub 3-1.

Synthesis of 2-18

Sub 3-2 (7.8g, 24mmol) was dissolved in toluene, Sub 5-1 (4.7g, 20mmol) was added and 9.3g (yield: 81%) of the final compound was obtained using the same synthesis method as in 5-17. Got it.

[Final product 3, 4 Synthesis Example: Path (2)]

Product 3.4 of Scheme 1 may be synthesized by, but are not limited to, the reaction route of Scheme 7.

Scheme 7

Synthesis Example of 3-19

Sub 6-1 Synthesis

Sub A (3) -1 (32.7g, 0.11mol) and Sub 5-1 (22.0g, 0.13mol) were prepared using the same synthesis method as Sub 2-1, Sub 6-1 (28.9g, 77%). Got.

Sub 7-1 Synthesis

Sub 6-1 (28.7 g, 0.08 mol) is dissolved in acetic acid, and hydrogen peroxide dissolved in acetic acid is dropped dropwise and stirred at room temperature for 6 hours. When the reaction was terminated by removing the acetic acid (acetic acid) using a reduced pressure device and separated by column chromatography to give the desired Sub 7-1 (24.0g, 80%).

3-19 Synthesis

Sub 7-1 (25.0 g, 0.07 mol) was added to an excess of trifluoromethanesulfonic acid, and stirred at room temperature for 24 hours. Then, water and pyridine (8: 1) were added. Add slowly and reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated using column chromatography to obtain 16.6 g of the desired 3-19. (Yield 73%)

Example of Synthesis of 8-20

Sub 6-2 Synthesis

Sub A (4) -1 (35.7 g, 0.11 mol) and Sub 5-2 (21.8 g, 0.13 mol) were prepared using the same synthesis method as Sub 2-1, Sub 6-2 (29.1 g, 72%). Got.

Sub 7-2 Synthesis

Sub 6-2 (29.0g, 0.08mol) was obtained by the same synthesis method as in Sub 7-1, to obtain the desired Sub 7-2 (23.9g, 79%).

8-20 Synthesis

The obtained Sub 7-2 (23.8g, 0.06mol) was obtained by the same method as the above 3-19 to obtain 15.7g of the desired 8-2. (Yield 72%)

[Final product 5, 6 Synthesis Example: Path (3)]

Product 5, 6 of Scheme 1 may be synthesized by the reaction route of Scheme 8, but is not limited thereto.

Scheme 8

Synthesis Example of 1-15

Sub 9-1 Synthesis

Sub A (1) -2 (58.1 g, 0.11 mol) and Sub 8-1 (17.9 g, 0.13 mol) were prepared using the same synthesis method as Sub 2-1, Sub 9-1 (39.9 g, 67%). Got.

1-15 Synthesis

The insert with obtained in Synthesis Sub 9-1 (5.4g, 10mmol) of _{Pd (OAc) 2 (0.2g,} 1mmol) in a round bottom flask, 3-nitropyridine (0.1g, 1mmol) ₆ C ₆ F (15ml) After dissolving with DMI (10ml), tert- butyl peroxybenzoate (3.92g, 21 mmol) was added and stirred at 90 ° 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 2.5g (yield: 46%).

Synthesis Example of 6-13

Sub 9-2 Synthesis

Sub A (2) -2 (37.5g, 0.11mol) and Sub 8-2 (17.9g, 0.13mol) were prepared using the same synthesis method as Sub 2-1, Sub 9-2 (25.2g, 70%). Got.

6-13 Synthesis

Sub 9-2 (3.3 g, 10 mmol) obtained in the above synthesis was obtained in the same manner as in 6-13, to obtain 1.7 g of the desired product (yield: 51%).

[Final product 7, 8 Synthesis Example: Path (4)]

Product 7, 8 of Scheme 1 may be synthesized by the reaction route of Scheme 8, but is not limited thereto.

Scheme 8

Synthesis Example of 7-21

Sub 10-1 Synthesis

Sub A (3) -1 (32.8g, 0.11mol) and Sub 10-1 (23.4g, 0.13mol) were prepared using the same synthesis method as Sub 2-1, Sub 11-1 (28.4g, 73%) Got.

7-21 Synthesis

Sub 11-1 (21.6g, 61mmol) obtained in the above synthesis was dissolved in THF (305ml) in a round bottom flask, methylmagnesium bromide 1.0M in THF (243.2ml, 243.21 mmol) was slowly added dropwise and stirred at room temperature. . After the reaction was completed, the mixture was extracted with diethyl ether and water, the organic layer was dried over MgSO ₄ and concentrated to give an intermediate product. This intermediate product was dissolved in acetic acid solution (250ml) and refluxed after addition of HCl (5ml). After the reaction was completed, water was added and the resulting solid was filtered under reduced pressure, washed with water and methanol to obtain 14.7 g (yield: 72% over two steps) as a white powder.

Synthesis Example of 4-23

Sub 11-2 Synthesis

Sub A (4) -2 (35.6 g, 0.11 mol) and Sub 10-2 (23.5 g, 0.13 mol) were prepared using the same synthesis method as Sub 2-1, Sub 11-2 (31.3 g, 75%). Got.

4-23 Synthesis

Sub 11-2 (23.1 g, 61 mmol) obtained in the above synthesis was obtained in the same manner as in 7-21, to obtain 22.5 g (yield: 76% over two steps) of 4-23.

Synthesis Example of 9-1

Sub B-2 Synthesis

Sub B-1 (12 g, 38.19 mmol), starting material, was dissolved in THF (168 ml) in a round bottom flask, followed by (4- (9- (4-([1,1'-biphenyl] -4-yl)- 6-phenyl-1,3,5-triazin-2-yl) -9H-carbazol-2-yl) -2- (methylthio) phenyl) boronic acid (24.46g, 38.19mmol), Pd (PPh ₃ ) ₄ ( 1.32 g, 1.15 mmol), K ₂ CO ₃ (15.84 g, 114.58 mmol), water (ml) were added and stirred at 90 ° 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 21.87 g (yield: 69%) of the product.

Sub B-3 Synthesis

Sub B-2 (21.8 g, 26.26 mmol), H ₂ O ₂ (2.23g, 65.66mmol) and acetic acid (131ml) were added to a round bottom flask and stirred at room temperature. After the reaction was completed, acetic acid was removed, water was added to obtain a solid, and the solid was dissolved in CH ₂ Cl ₂ , silicagel column, and concentrated to obtain 18 g of a product. (Yield 81%)

9-1 Synthesis

Sub B-3 (18g, 21.28mmol) was dissolved in an excess of H ₂ SO ₄ (43ml) in a round bottom flask and stirred at 40 ^° C. Upon completion of the reaction, the mixture was neutralized to pH 8-9 with 0.2 N aqueous NaOH solution. Water was removed under reduced pressure, extracted with CH ₂ Cl ₂ , concentrated, and silicagel column and recrystallization to give the product 6.75g. (Yield 39%)

Synthesis Example of 9-4

Sub B-5 Synthesis

Starting materials Sub B-4 (10 g, 33.54 mmol), THF (148 ml), (5- (9- (4-([1,1'-biphenyl] -4-yl) benzo [h] quinazolin-2- yl) -9H-carbazol-3-yl) -2- (methylthio) phenyl) boronic acid (22.26g, 33.54mmol), Pd (PPh ₃ ) ₄ (1.16 g, 1.01 mmol), K ₂ CO ₃ (13.91 g, 100.62 mmol), and water (74 ml) were obtained by 20.49 g (yield: 73%) of the product using the synthesis method of B-2.

Sub B-6 Synthesis

Sub B-5 (20.2 g, 24.13 mmol), H ₂ O ₂ 17.098 g of (2.05 g, 60.33 mmol) and acetic acid (121 ml) were obtained using the B-3 synthesis method. (Yield 83%)

9-4 Synthesis

Sub B-6 (17 g, 19.93 mmol) and H ₂ SO ₄ (40 ml) were obtained using 7.09 g of the product using the above-described 9-1 synthesis method. (Yield 43%)

Synthesis Example of 9-9

Sub B-8 Synthesis

Starting materials Sub B-7 (10.5g, 32.39mmol), THF (142ml), (2- (methoxycarbonyl) -4- (9- (4-phenylbenzofuro [3,2-d] pyrimidin-2-yl)- 9H-carbazol-3-yl) phenyl) boronic acid (19.09g, 32.39mmol), Pd (PPh ₃ ) ₄ (1.12 g, 0.97 mmol), K ₂ CO ₃ (13.43 g, 97.16 mmol), and water (71 ml) were obtained using 15.84 g (yield: 62%) of the product using the synthesis method of B-2.

9-9 Synthesis

Sub B-8 (15.50, 19.65mmol) was dissolved in THF (98ml) in a round bottom flask, methylmagnesium bromide (9.37g, 78.59mmol) was slowly added dropwise and stirred at room temperature. After the reaction was completed, the mixture was extracted with diethyl ether and water, the organic layer was dried over MgSO ₄ and concentrated to give an intermediate product. This intermediate product was dissolved in acetic acid solution (79 ml) and refluxed after addition of HCl (2 ml). After the reaction was completed, water was added and the resulting solid was filtered under reduced pressure, washed with water and methanol to obtain 6.82 g (yield: 45% over two steps) as a white powder.

Manufacturing Evaluation of Organic Electrical Device

Example 1 Fabrication and Test of Red Organic Light-Emitting Device

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, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPB) was vacuum-deposited to a thickness of 60 nm as a hole transporting compound on the membrane to form a hole transport layer. Formed. The invention compound represented by the formula (1) was used as a host on the hole transport layer, and as a dopant, (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] was 95: 5 A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping. 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. Thereafter, 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] to [Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compounds A to E were used as host materials.

As can be seen from the results of Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a phosphorescent host can significantly improve luminous efficiency, lifetime and driving voltage.

In other words, Comparative Compounds B to E having 6-membered heterocycles as cores compared to Comparative Compound A, which is generally used as a host material, showed improved device results, and 6-membered heterocycles such as Compounds B to E showed improved results. The compound of the present invention in which N is substituted shows the best device result with the lowest driving voltage, maximizing efficiency and lifetime.

This is because the LUMO energy value is relatively low as N is substituted with one or more N-membered heterocyclic cores, thereby easily receiving electrons in the electron transport layer, thereby improving charge balance in the light emitting layer, resulting in low driving voltage and high efficiency and lifetime. It seems to have caused the result. Therefore, this suggests that one or more N is substituted in the 6-ring heterocyclic core, and that the chemical and physical properties of the N-substituted compound may be significantly different.

As described above, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a phosphorescent host can significantly improve luminous efficiency, lifetime and driving voltage. In addition, the organic electroluminescent device using the organic electroluminescent device material of the present invention in at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer and an electron transport layer is also luminous efficiency, life and The voltage can be significantly improved.

The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications can be made without departing from the essential features 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 scope of protection of the present invention should be interpreted by the following claims, and all descriptions within the equivalent scope should be construed as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority to Korean Patent Application No. 10-2016-0017658 filed with Korea on February 16, 2016 and Patent Application No. 10-2017-0000273 filed with Korea on January 2, 2017. The contents of which are hereby incorporated by reference in their entirety. In addition, if this patent application claims priority for the same reason as above for other countries, all the contents are incorporated into this patent application by reference.

Claims (11)

1. Compound represented by the following formula (1)

       Formula (1)

   

   1) X is ^one of NR ¹ , S, O, CR'R ”,

   2) n and m are 0 or 1, n + m is 1 or more,

    (Where n and m are 0, A and B are single bonds to form pentagonal rings)

   3) A and B are each independently a single bond, NR ¹ , S, O, CR'R ”,

   4) Z ¹ to Z ¹² are each independently CR ² , N and at least one is N,

   5) R ¹ and R ² are independently of each other 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 );

   (Wherein L ′ is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; and C ₂ ~ C ₆₀ heterocyclic group; selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Selected from the group consisting of a fused ring group of an aromatic ring of C and a C ₂ ~ C ₆₀ hetero ring group containing at least one hetero atom of O, N, S, Si and P), or adjacent R ¹ , Adjacent R ² may combine with each other to form a ring,

   When at least two of Z ¹ to Z ¹² are CR ² , each CR ² may be independently of each other, and each CR ² may be the same or different.

   6) R ', R "is hydrogen, an alkyl group of C ₁ ~ C ₅₀ ; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of, can be combined with each other to form a spiro compound,

   When the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, arylene group, fluorenylene group, each of these are 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; 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 when these substituents are adjacent to each other they may combine with each other to form a ring.
2. The method of claim 1,

   A compound represented by the formula (1) is represented by the following formulas (2) to (3).

   

   Z ¹ to Z ¹² , X, A, and B are the same as Z ¹ to Z ¹² , X, A, and B defined in Chemical Formula (1).
3. The method of claim 1,

   A compound represented by the formula (1) is represented by the following formulas (4) to (11).

   

   Z ¹ to Z ¹² , R ′, R ″, A, and B are the same as Z ¹ to Z ¹² , R ′, R ″, A, and B defined in Chemical Formula (1).
4. The method of claim 1,

   The compound represented by General formula (1) is represented as follows.

   

   

   

   

   

   

   

   

   

   
5. A first electrode;

   Second electrode; And

   An organic electric device comprising: an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 1 to 4.
6. The method of claim 5,

   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, an electron transport auxiliary layer and an electron transport layer of the organic material layer, the compound is a single compound or two or more compounds of the mixture An organic electric element comprising as a component.
7. The method of claim 5,

   And the compound is used as a phosphorescent host material of the light emitting layer.
8. The method of claim 5,

   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.
9. The method of claim 5,

   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.
10. A display device comprising the organic electroluminescent device of claim 5; And

    And a controller for driving the display device.
11. The method of claim 10,

    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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