KR102342339B1 - Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same - Google Patents

Abstract

상기 화학식 A에서 X₁, X₂, L₁, L₂ 및 R은 발명의 상세한 설명에 기재된 바와 같다. The present invention relates to an anthracene derivative represented by the following [Formula A] and an organic light emitting device comprising the same.
[Formula A]

In Formula A, X ₁ , X ₂ , L ₁ , L ₂ and R are as described in the detailed description of the invention.

Description

Compound for organic light-emitting device and organic light-emitting device including the same

The present invention relates to a compound for an organic light emitting device capable of realizing an organic light emitting device with a low driving voltage, and an organic light emitting device including the same, and more particularly, when used as a fluorescent host, excellent device characteristics through a low driving voltage It relates to a compound for an organic light emitting device that can be implemented and an organic light emitting device including the same.

An organic light emitting diode (OLED) is a display using a self-luminescence phenomenon, has a large viewing angle, can be lightweight and compact compared to a liquid crystal display, and has advantages such as a fast response speed. ) is expected to be applied to displays or lighting.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their functions. The light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. . In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is decreased due to the emission attenuation effect. Therefore, increase in color purity and energy A host-dopant system can be used as a luminescent material to increase the luminous efficiency through transition.

The principle is that when a small amount of a dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transported to the dopant to emit light with high efficiency. In this case, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used.

As a prior art related to the host compound among these light emitting layers, Korean Patent Publication No. 10-0910150 (2009.08.03) relates to an organic light emitting device including a compound in which a heterocyclic substituent is bonded to the terminal of an anthracene structure in a light emitting medium layer. This is described, and in Japanese Patent Publication No. 5608978 (October 22, 2014), a technology related to an organic light emitting device including an anthracene derivative in which a substituent of a dibenzofuran structure is bonded to the terminal of an anthracene structure in a light emitting medium layer is described. have.

However, in the prior art, including the prior art, although various kinds of compounds for use in the light emitting layer have been prepared, it is still possible to drive the organic light emitting device at a lower voltage. Development of a material that can be used for the light emitting layer in the organic light emitting device The necessity of this is constantly being demanded.

Registered Patent Publication No. 10-0910150 (2009.08.03)

Japanese Patent Publication No. 5608978 (2014.10.22)

Accordingly, the first technical problem to be achieved by the present invention is to provide a compound for an organic light emitting device that can be used as a host in a light emitting layer in an organic light emitting device and can be driven at a low voltage.

A second technical problem to be achieved by the present invention is to provide an organic light emitting device including the compound.

The present invention provides an anthracene derivative represented by the following [Formula A] in order to achieve the first technical object.

[Formula A]

In the [Formula A],

L ₁ and L ₂ are the same or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms, a substituted or unsubstituted and hetero atom, any one selected from O, N, S and Si a heteroarylene group having 2 to 50 carbon atoms having the above;

Substituent R is a deuterium atom, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 alkoxy group, a substituted or unsubstituted C Any one selected from a 6 to 30 aryloxy group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a cyano group, and a halogen group;

m is an integer from 1 to 8, and when m is 2 or more, each R is the same as or different from each other,

Hydrogen is substituted at the aromatic carbon of the anthracene ring to which R is not bonded,

X ₁ and X ₂ are each the same or different, and each independently represent a substituent represented by the following Structural Formula A, at least one of which is a substituent represented by the following Structural Formula B or C;

[Structure A]

[Formula B] [Formula C]

In the above Structural Formulas A to C

Each of the substituents R ₁ to R ₇ , R ₁₁ to R ₁₈ are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to 30 C group An alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted C1 to 30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthiooxy group, a substituted or An unsubstituted C 1 to C 30 alkylamine group, a substituted or unsubstituted C 5 to C 30 arylamine group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted and heteroatom O, N or Having S, a heteroaryl group having 2 to 50 carbon atoms, a cyano group, a nitro group, a halogen group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted germanium group having 1 to 30 carbon atoms, substituted or unsubstituted A cyclic boron group having 1 to 30 carbon atoms, a substituted or unsubstituted aluminum group having 1 to 30 carbon atoms, a carbonyl group, a phosphoryl group, an amino group, a thiol group, a hydroxyl group, a selenium group, a tellurium group, an amide group, an ether group and an ester group Any one selected from

In Structural Formula A, _{one of R 15} to R ₁₈ is a single bond bonded to a linking group L ₁ or L _{2 ,}

'***' in Structural Formulas B and C may be a binding site binding to the _{linking group L 1} or L _{2 .}

In addition, the present invention to achieve the second object, a first electrode; a second electrode opposite to the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one organic light emitting compound of the present invention.

According to the present invention, the organic light emitting compound represented by [Formula A] has excellent characteristics that enable driving of the organic light emitting device at a lower voltage than the organic light emitting compound according to the prior art.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides an anthracene compound represented by the following [Formula A] as a novel aromatic organic light emitting compound.

[Formula A]

In the [Formula A],

L ₁ and L ₂ are the same or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms, a substituted or unsubstituted and hetero atom, any one selected from O, N, S and Si a heteroarylene group having 2 to 50 carbon atoms having the above;

Substituent R is a deuterium atom, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 alkoxy group, a substituted or unsubstituted C Any one selected from a 6 to 30 aryloxy group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a cyano group, and a halogen group;

m is an integer from 1 to 8, and when m is 2 or more, each R is the same as or different from each other,

Hydrogen is substituted at the aromatic carbon of the anthracene ring to which R is not bonded,

X ₁ and X ₂ are each the same or different, and each independently represent a substituent represented by the following Structural Formula A, at least one of which is a substituent represented by the following Structural Formula B or C;

[Structure A]

[Formula B] [Formula C]

In the above Structural Formulas A to C

Each of the substituents R ₁ to R ₇ , R ₁₁ to R ₁₈ are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to 30 C group An alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted C1 to 30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthiooxy group, a substituted or An unsubstituted C 1 to C 30 alkylamine group, a substituted or unsubstituted C 5 to C 30 arylamine group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted and heteroatom O, N or Having S, a heteroaryl group having 2 to 50 carbon atoms, a cyano group, a nitro group, a halogen group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted germanium group having 1 to 30 carbon atoms, substituted or unsubstituted A cyclic boron group having 1 to 30 carbon atoms, a substituted or unsubstituted aluminum group having 1 to 30 carbon atoms, a carbonyl group, a phosphoryl group, an amino group, a thiol group, a hydroxyl group, a selenium group, a tellurium group, an amide group, an ether group and an ester group Any one selected from

In Structural Formula A, _{one of R 15} to R ₁₈ is a single bond bonded to a linking group L ₁ or L _{2 ,}

'***' in Structural Formulas B and C is a binding site that binds to a _{linking group L 1} or L _{2 ,}

'Substitution' in 'substituted or unsubstituted' in [Formula A] is deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, a carbon number A 1 to 24 alkenyl group, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or 2 carbon atoms to 24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 heteroarylamino group, C1-C24 alkylsilyl group, carbon number It means being substituted with one or more substituents selected from the group consisting of an arylsilyl group having 1 to 24 and an aryloxy group having 1 to 24 carbon atoms.

In the present invention, considering the range of the alkyl group or aryl group in the "substituted or unsubstituted C1-C24 alkyl group", "substituted or unsubstituted C6-C24 aryl group", etc., the C1 The ranges of the carbon number of the alkyl group having to 24 and the aryl group having 6 to 24 carbon atoms refer to the total number of carbon atoms constituting the alkyl or aryl portion when viewed as unsubstituted without considering the substituted portion of the substituent. For example, a phenyl group substituted with a butyl group at the para-position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

On the other hand, the aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members. In addition, when the aryl group has a substituent, it may be fused with a neighboring substituent to further form a ring.

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, and aromatic groups such as pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., wherein at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom , a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R''), R' and R" are each independently of each other having 1 to 10 carbon atoms an alkyl group, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms. of an alkenyl group, a C1-C24 alkynyl group, a C1-C24 heteroalkyl group, a C6-C24 aryl group, a C6-C24 arylalkyl group, a C2-C24 heteroaryl group or a C2-C24 heteroaryl group It may be substituted with a heteroarylalkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, includes 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms are carbon atoms It means a ring aromatic system having 2 to 24 carbon atoms, The rings may be fused to form a ring. And one or more hydrogen atoms in the heteroaryl group may be substituted with the same substituents as in the case of the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, and at least one hydrogen atom of the alkyl group is Atoms can be substituted with the same substituents as in the case of the above aryl group.

Specific examples of the alkoxy group as a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. One or more hydrogen atoms in the alkoxy group may be substituted with the same substituents as in the case of the aryl group.

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclo butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

In the compound represented by Formula A in the present invention, the linking _{groups L 1} and L ₂ bonded to positions 9 and 10 of the anthracene ring are each connected to a substituent having the above Structural Formula A, and among _{the linking groups L 1} and L ₂ As shown in Figure 1 below, at least one of the substituted or unsubstituted dibenzofuran is characterized in that it bonds to the carbon atom at the 1st or 2nd position of the phenyl ring of either one of the phenyl rings.

[그림 1]

[Figure 1]

In the present invention, when the compound represented by Formula A is used as a host material in the light emitting layer of the organic light emitting device, the resulting organic light emitting device may exhibit a low driving voltage.

In the present invention, each of the connecting _{groups L 1} and L ₂ may be a single bond or any one selected from the following [Structural Formula 1] to [Structural Formula 9].

[Structural formula 1] [Structural formula 2] [Structural formula 3] [Structural formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7] [Structural formula 8]

[Structural Formula 9]

Hydrogen or deuterium may be bonded to the carbon site of the aromatic ring in [Structural Formula 1] to [Structural Formula 9].

In addition, in the present invention, _{at least one of the substituents R 11} to R ₁₈ in Structural Formula A is any one selected from the following [Structural Formula 21] to [Structural Formula 31], or the substituents R ₁ to in Structural Formulas B and C At least one of R ₇ is any one selected from the following [Structural Formula 21] to [Structural Formula 31], or the linking group L ₁ or L ₂ is a substituent, any one selected from the following [Structural Formula 21] to [Structural Formula 31] may include

[Structural formula 21] [Structural formula 22] [Structural formula 23] [Structural formula 24]

[Structural formula 25] [Structural formula 26] [Structural formula 27] [Structural formula 28]

[Structural formula 29] [Structural formula 30] [Structural formula 31]

Hydrogen or deuterium may be bonded to the carbon site of the aromatic ring in the [Structural Formula 21] to [Structural Formula 31].

That is, in the anthracene derivative represented by Formula A in the present invention, at least one of the substituents bonded to the phenyl ring of dibenzofuran is any one selected from the above [Formula 21] to [Formula 31], or the linking group L ₁ or L ₂ is a substituent, including any one selected from the following [Structural Formula 21] to [Structural Formula 31], wherein L ₁ or L ₂ is a fluorine group; cyano group; biphenyl group; or a phenyl group in which at least one selected from a fluorine group and a cyano group is substituted; or a naphthyl group in which at least one selected from a fluorine group and a cyano group is substituted; Alternatively, a biphenyl group in which at least one selected from a fluorine group and a cyano group is substituted may be included as a substituent.

Meanwhile, in the present invention, the substituent R in Formula A is a deuterium atom, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 50 It is selected from aryl groups, and m may be an integer of 1 to 4.

In addition, in the present invention, the anthracene derivative represented by Formula A may be a compound having an asymmetric structure based on a straight line consisting _{of L 1} -anthracene-L _{2 in the molecular structure shown in Figure 2 below.}

[그림 2]

[Figure 2]

Hereinafter, any one compound selected from the group represented by the following [Compound 1] to [Compound 21] is shown as a representative structural formula of the organic light emitting compound of the present invention, but the compounds according to the present invention are not limited thereto.

<Compound 1> <Compound 2> <Compound 3>

<Compound 4> <Compound 5> <Compound 6>

<Compound 7> <Compound 8> <Compound 9>

<Compound 10> <Compound 11> <Compound 12>

<Compound 13> <Compound 14> <Compound 15>

<Compound 16> <Compound 17> <Compound 18>

<Compound 19> <Compound 20> <Compound 21>

In addition, the present invention is a first electrode; a second electrode opposite to the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one anthracene derivative represented by Formula A in the present invention.

In the present invention, "(organic layer) includes one or more compounds" means "(organic layer) may include one compound belonging to the scope of the present invention or two or more different compounds belonging to the scope of the compound. can be interpreted as "there is

In this case, the organic layer containing the compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer.

In addition, in the present invention, the organic layer interposed between the first electrode and the second electrode may be a light emitting layer, in this case, the light emitting layer consists of a host and a dopant, and the compound of Formula A may be used as a host.

In this case, specific examples of the dopant material used in the light emitting layer include a pyrene compound, a deuterium substituted pyrene compound, an arylamine, a deuterium substituted arylamine, a peryl compound, a deuterium substituted peryl compound, a pyrrole compound, Deuterium substituted pyrrole compound, hydrazone compound, deuterium substituted hydrazone compound, carbazole compound, deuterium substituted carbazole compound, stilbene compound, deuterium substituted stilbene compound, starburst compound, deuterium substituted starburst compounds, oxadiazole compounds, deuterium substituted oxadiazole compounds, coumarin, deuterium substituted coumarin, and the like may be mentioned, but the present invention is not limited thereto.

When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

In addition, in the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer and an electron injection layer is formed by a single molecule deposition method or a solution process can be Here, the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is to form each layer It refers to a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device in the present invention is a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; And monochromatic or white flexible lighting device; may be used in any one device selected from.

As a specific example of the present invention, a hole transport layer (HTL, Hole Transport Layer) is additionally stacked between the anode and the organic light emitting layer, and an electron transport layer (ETL, Electron Transport Layer) is added between the cathode and the organic light emitting layer. can be stacked with

As a material of the hole transport layer, electron-donating molecules with a small ionization potential are used, and diamine, triamine, or tetraamine derivatives having triphenylamine as a basic skeleton are often used, for example, N,N'-bis (3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N '-diphenylbenzidine (a-NPD) or the like can be used.

A hole injection layer (HIL, Hole Injecting Layer) may be further laminated on the lower portion of the hole transport layer, and the hole injection layer material is also not particularly limited as long as it is commonly used in the art. For example, CuPc(copperphthalocyanine) or starburst amines TCTA(4,4',4"-tri(N-carbazolyl)triphenyl-amine), m-MTDATA(4,4',4"-tris-(3-methylphenylphenyl) amino) triphenylamine) and the like can be used.

In addition, as the material for the electron transport layer, for example, PBD, BMD, BND or Alq _{3 which} are oxadiazole derivatives may be used.

On the other hand, an electron injection layer (EIL) that facilitates electron injection from the cathode and ultimately improves power efficiency may be further laminated on the electron transport layer, the electron injection layer material Also, as long as it is conventionally used in the art, it may be used without any particular limitation, and for example, _{a material such as LiF, NaCl, CsF, Li 2} O, and BaO may be used.

Hereinafter, an organic light emitting device of the present invention will be described with reference to FIG. 1 .

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, a hole injection layer 30 and electrons. The injection layer 70 may be further included, and in addition to that, it is also possible to further form an intermediate layer of one or two layers.

Referring to FIG. 1, an organic light emitting diode and a manufacturing method thereof of the present invention will be described as follows. First, the anode 20 is formed by coating a material for an anode electrode on the substrate 10 . Here, as the substrate 10, a substrate used in a conventional organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

A hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30 .

Subsequently, an organic light emitting layer 50 is laminated on the hole transport layer 40 and a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film. can do. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but has an electron transport ability and has an ionization potential higher than that of a light emitting compound, and typically BAlq, BCP, TPBI, or the like may be used.

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a metal for forming a cathode is vacuum heated on the electron injection layer 70 . By vapor deposition to form the cathode 80 electrode, the organic EL device is completed. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

In addition, according to a specific example of the present invention, it is preferable that the thickness of the light emitting layer is 50 to 2,000 Å, and the light emitting layer may consist of a host and a dopant, and the compound of the present invention may be used as a host.

In this case, the dopant may be a compound represented by the following [Formula 1] or [Formula 2]. In this case, the light emitting layer may further include various dopant materials.

[Formula 1] [Formula 2]

Among the [Formula 1] and [Formula 2],

A is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms , It may be any one selected from a C3 to C50 heteroarylene group, which is substituted or unsubstituted and has O, N or S as a hetero atom.

More specifically, A is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a single bond, preferably anthracene, pyrene, phenanthrene, indenophenanthrene, chrysene, naphthacene, picene, triphenyl It may be any one of ene, perylene, and pentacene, and more specifically, A may be a substituent represented by any one of Chemical Formulas A1 to A10 below.

[Formula A1] [Formula A2] [Formula A3]

[Formula A4] [Formula A5] [Formula A6]

[Formula A7] [Formula A8] [Formula A9]

[Formula A10]

_{wherein Z 1} to Z ₂ of [Formula A3] are hydrogen, a deuterium atom, a substituted or unsubstituted C 1 to C 60 alkyl group, a substituted or unsubstituted C 2 to C 60 alkenyl group, a substituted or unsubstituted C 2 to 60 alkynyl group, substituted or unsubstituted C 1 to C 60 alkoxy group, substituted or unsubstituted C 1 to C 60 alkylthio group, substituted or unsubstituted C 3 to C 60 cycloalkyl group, substituted Or an unsubstituted C6 to C60 aryl group, a substituted or unsubstituted C5 to C60 aryloxy group, a substituted or unsubstituted C5 to C60 arylthio group, a substituted or unsubstituted C2 to C60 A heteroaryl group, a substituted or unsubstituted (alkyl)amino group having 1 to 60 carbon atoms, a di(substituted or unsubstituted alkyl having 1 to 60 carbon atoms)amino group, or a (substituted or unsubstituted C6 to C60 aryl)amino group , at least one selected from the group consisting of a di(substituted or unsubstituted aryl)amino group having 6 to 60 carbon atoms, Z ₁ to Z ₂ Each may be the same or different from each other, and may form a condensed ring with a group adjacent to each other .

In addition, in [Formula 1],

Wherein X ₁ and X ₂ are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a single bond, and X ₁ and X ₂ may be bonded to each other,

wherein Y ₁ and Y ₂ are each independently a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C2-C24 heteroaryl group, a substituted or unsubstituted C1-C24 alkyl group, substituted Or an unsubstituted C1-C24 heteroalkyl group, a substituted or unsubstituted C3-C24 cycloalkyl group, a substituted or unsubstituted C1-C24 alkoxy group, a cyano group, a halogen group, a substituted or unsubstituted carbon number 1 from the group consisting of a 6 to 24 aryloxy group, a substituted or unsubstituted C 1 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C 30 arylsilyl group, germanium, phosphorus, boron, deuterium and hydrogen. More than one species is selected, and _{each of Y 1} to Y ₂ is the same as or different from each other, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

Each of l and m is an integer of 1 to 20, and n is an integer of 1 to 4.

In addition, in [Formula 2],

C _y is a substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms, b is an integer of 1 to 4, but when b is 2 or more, each cycloalkane may be in a fused form, and the substituted hydrogen is Each may be substituted with deuterium or alkyl, and may be the same as or different from each other.

Also above B is a single bond or -[C(R ₅ )(R ₆ )] _p -, wherein p is an integer from 1 to 3, but when p is 2 or more, 2 or more R ₅ and R ₆ are the same or different from each other;

Wherein R ₁ , R ₂ , R _{3 ,} R ₅ and R ₆ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or A salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms , a substituted or unsubstituted C 1 to C 60 alkoxy group, a substituted or unsubstituted C 1 to C 60 alkylthio group, a substituted or unsubstituted C 3 to C 60 cycloalkyl group, a substituted or unsubstituted C 6 to 60 aryl group, substituted or unsubstituted C5 to C60 aryloxy group, substituted or unsubstituted C5 to C60 arylthio group, substituted or unsubstituted C2 to C60 heteroaryl group, substituted Or an unsubstituted (alkyl)amino group having 1 to 60 carbon atoms, di(substituted or unsubstituted alkyl)amino group having 1 to 60 carbon atoms, or (substituted or unsubstituted aryl)amino group having 6 to 60 carbon atoms, di(substituted or It may be selected from an unsubstituted C 6 to C 60 aryl) amino group, a substituted or unsubstituted C 1 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C 30 arylsilyl group, germanium, phosphorus, and boron, ,

a is an integer of 1 to 4, but when a is 2 or more, 2 or more R ₃ are the same or different from each other, and when R ₃ is plural, each R ₃ may be in a fused form, and n is 1 to 4 is an integer

In addition, the amine group bonded to A in [Formula 1] and [Formula 2] may be represented by any one selected from the group represented by the following [Substituent 1] to [Substituent 52], but is not limited thereto.

[Substitute 1] [Substitute 2] [Substitute 3]

[Substitute 4] [Substitute 5] [Substitute 6]

[Substitute 7] [Substitute 8] [Substitute 9]

[Substituent 10] [Substituent 11] [Substituent 12]

[Substituent 13] [Substitute 14] [Substitute 15]

[Substitute 16] [Substitute 17] [Substitute 18]

[Substituent 19] [Substituent 20] [Substituent 21]

[Substituent 22] [Substituent 23] [Substituent 24]

[Substitute 25] [Substitute 26] [Substitute 27]

[Substitute 28] [Substitute 29] [Substitute 30]

[substituent 31] [substituent 32] [substituent 33]

[Substitute 34] [Substitute 35] [Substitute 36]

[Substituent 37] [Substitute 38] [Substitute 39]

[Substitute 40] [Substitute 41] [Substitute 42]

[substituent 43] [substituent 44] [substituent 45]

[Substitute 46] [Substitute 47] [Substitute 48]

[Substitute 49] [Substitute 50] [Substitute 51]

[Substitute 52]

In the above substituents, R is the same as or independently from each other, hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted C 1 to C 60 alkyl group, a substituted or unsubstituted C 2 to C 60 alkenyl group, a substituted or unsubstituted C 2 to C 60 alkynyl group, a substituted or unsubstituted C 1 to C 1 60 alkoxy group, substituted or unsubstituted C 1 to C 60 alkylthio group, substituted or unsubstituted C 3 to C 60 cycloalkyl group, substituted or unsubstituted C 6 to C 60 aryl group, substituted or An unsubstituted C5 to C60 aryloxy group, a substituted or unsubstituted C5 to C60 arylthio group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstituted C1 to C60 (alkyl) amino group, di(substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, or (substituted or unsubstituted aryl having 6 to 60 carbon atoms) amino group, di(substituted or unsubstituted aryl having 6 to 60 carbon atoms) ) may be selected from an amino group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C30 arylsilyl group, germanium, phosphorus, and boron, each of which may be substituted by 1 to 12 and each substituent may form a condensed ring with a group adjacent to each other.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereby.

Synthesis Example 1: Synthesis of compound 3

Synthesis Example 1-(1): Synthesis of Intermediate 1-a

According to Scheme 1 below, Intermediate 1-a was synthesized:

<Scheme 1>

<Intermediate 1-a>

In a 2L round-bottom flask reactor, 4-bromodibenzofuran (193.0g, 0.781mol), acetamide (69.2g, 1.172mol), copper iodide (74.38g, 0.390 mol), (ㅁ)trans-1,2-di Aminocyclohexane (89.2 g, 0.781 mol), potassium carbonate (218.91 g, 1.56 mol), and 1540 mL of toluene were added, and the mixture was stirred under reflux overnight under a nitrogen stream. When the reaction was completed, the mixture was filtered through a Celite pad and washed with hot toluene until no product came out. The filtrate was concentrated under reduced pressure and crystallized by adding acetonitrile. The resulting solid was filtered to obtain <Intermediate 1-a>. (76.0 g, 43%)

Synthesis Example 1-(2): Synthesis of Intermediate 1-b

Intermediate 1-b was synthesized according to Scheme 2:

<Scheme 2>

<Intermediate 1-a> <Intermediate 1-b>

In a 2L round-bottom flask reactor, <Intermediate 1-a> (78.2g, 0.347mol) and 700ml of acetic acid were put and dissolved. 300 ml of acetic acid and bromine (55.2 g, 0.347 mol) were mixed and added dropwise to the reaction solution. After confirming the completion of the reaction by thin film chromatography while stirring at room temperature, 500 ml of ethanol was added, stirred, and then filtered. The solid was stirred in 500 ml of ethanol and filtered to obtain <Intermediate 1-b>. (86.0g, 80%)

Synthesis Example 1-(3): Synthesis of Intermediate 1-c

Intermediate 1-c was synthesized according to Scheme 3:

<Scheme 3>

<Intermediate 1-b> <Intermediate 1-c>

In a 2L round-bottom flask reactor, <Intermediate 1-b> (86.0 g, 0.283 mol), 600 ml of ethanol, 430 ml of tetrahydrofuran, and potassium hydroxide (47.6 g, 0.848 mol) were dissolved in 260 ml of water. The reaction solution was stirred at reflux overnight. After completion of the reaction, it was cooled to room temperature. It was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and crystallized with ethanol. The resulting solid was filtered and washed with ethanol. The solid was recrystallized from methylene chloride and hexane to obtain <Intermediate 1-c>. (70.0 g, 93%)

Synthesis Example 1-(4): Synthesis of Intermediate 1-d

Intermediate 1-d was synthesized according to Scheme 4:

<Scheme 4>

<Intermediate 1-c> <Intermediate 1-d>

<Intermediate 1-c> (74.0 g, 0.282 mol), 90 ml of hydrochloric acid and 440 ml of water were added to a 2L round-bottom flask reactor, and the mixture was cooled to 0°C and stirred. To the cooled solution, sodium nitrite (25.3 g, 0.367 mol) was dissolved in 90 water and added dropwise. After stirring at the same temperature for one hour, potassium iodide (93.7 g, 0.565 mol) was dissolved in 90 ml of water and put into the reaction solution. At this time, care was taken not to exceed 5 degrees of the reaction solution, and after completion of the dropwise addition, the mixture was stirred at room temperature. After completion of the reaction, 400 ml of ethyl acetate was added and stirred. The organic layer was separated and concentrated under reduced pressure. The material was separated and purified by column chromatography, and recrystallized from methylene chloride and hexane to obtain <Intermediate 1-d>. (40.0 g, 40%)

Synthesis Example 1-(5): Synthesis of Intermediate 1-e

Intermediate 1-e was synthesized according to Scheme 5:

<Scheme 5>

<Intermediate 1-d> <Intermediate 1-e>

In a 250mL round-bottom flask reactor, <Intermediate 1-d> (10.0g, 27mmol), 3-fluorobenzeneboronic acid (4.5g, 32mmol), tetrakis(triphenylphosphine)palladium (0.6g, 1mmol), potassium Carbonate (7.4 g, 54 mmol) was added, and toluene 70 mL, methanol 30 mL, and water 20 mL were added. The temperature of the reactor was raised to 90 degrees and stirred overnight. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography. Recrystallization from methylene chloride and hexane gave <Intermediate 1-e>. (5.7 g, 60%)

Synthesis Example 1-(6): Synthesis of Intermediate 1-f

Intermediate 1-f was synthesized according to Scheme 6:

<Scheme 6>

<Intermediate 1-e> <Intermediate 1-f>

In a 500ml round-bottom flask reactor, <Intermediate 1-e> (17.3g, 0.051mol), bis(pinacolato)diboron (15.5g, 0.061mol), 1,1'-bis(diphenylphosphino)ferrocene- Palladium (II) dichloride (1.2 g, 0.002 mol), potassium acetate (14.9 g, 0.152 mol), and 175 ml of 1,4-dioxane were added and stirred under reflux overnight. After completion of the reaction, the filtrate was concentrated under reduced pressure by passing it through a celite pad. The material was separated and purified by column chromatography to obtain <Intermediate 1-f>. (15g, 76%)

Synthesis Example 1-(7): Synthesis of compound 3

Compound 3 was synthesized according to Scheme 7:

<Scheme 7>

<Intermediate 1-f> <Compound 3>

<Intermediate 1-f> (15.3 g, 39 mmol), 9,10-dibromoanthracene (5.5 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0.8 g, 1 mmol), Potassium carbonate (9.0 g, 65 mmol) was added, and toluene 40 mL, ethanol 17 mL, and water 11 mL were added. The temperature of the reactor was raised to 90 degrees and stirred overnight. When the reaction was completed, the temperature of the reactor was lowered to room temperature, and 100 ml of methanol was added to crystallize. The resulting solid was filtered and washed with water and acetone. Recrystallization from toluene and acetone gave compound 3 (3.0 g, 34 %).

MS (MALDI-TOF): m/z 699.2 [M ⁺ ]

Claims (11)

An anthracene derivative represented by the following [Formula A].
[Formula A]

In the [Formula A],
L ₁ and L ₂ are the same or different from each other, and are each independently any one selected from a single bond, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms;
Substituent R is a deuterium atom, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 silyl group, a cyano group, a halogen group Any one selected from
m is an integer from 0 to 8, and when m is 2 or more, each R is the same as or different from each other,
Hydrogen is substituted at the aromatic carbon of the anthracene ring to which R is not bonded,
X ₁ and X ₂ are each the same or different, and each independently represent a substituent represented by the following Structural Formula A, at least one of which is a substituent represented by the following Structural Formula B or C;

[Structure A]

[Formula B] [Formula C]
In the above Structural Formulas A to C
Each of the substituents R ₁ to R ₇ , R ₁₁ to R ₁₈ are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 A cycloalkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted C 2 to C 50 heteroaryl group having O, N or S as a heteroatom, a cyano group, a nitro group, a halogen group, a substituted or Any one selected from unsubstituted silyl groups having 1 to 30 carbon atoms,
At least one of the substituents R ₁₁ to R ₁₈ in Structural Formula A is any one selected from the following [Structural Formula 21] to [Structural Formula 30];
_{At least one of the substituents R 1} to R ₇ in Structural Formulas B and C is any one selected from the following [Structural Formula 21] to [Structural Formula 30],

[Structural formula 21] [Structural formula 22] [Structural formula 23] [Structural formula 24]

[Structural formula 25] [Structural formula 26] [Structural formula 27] [Structural formula 28]

[Formula 29] [Formula 30]
Hydrogen or deuterium may be bonded to the carbon position of the aromatic ring in the [Structural Formula 21] to [Structural Formula 30],
In Structural Formula A, _{one of R 15} to R ₁₈ is a single bond bonded to a linking group L ₁ or L _{2 ,}
'***' in Structural Formulas B and C is a binding site that binds to a _{linking group L 1} or L _{2 ,}
'Substitution' in 'substituted or unsubstituted' in [Formula A] is deuterium, a cyano group, a halogen group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, 6 to 24 carbon atoms of an aryl group, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 1 to 24 carbon atoms. It means to be substituted with one or more selected substituents. The method of claim 1,
The linking _{groups L 1} and L ₂ are each a single bond, or any one selected from the following [Structural Formula 1], [Structural Formula 2], [Structural Formula 4], [Structural Formula 6], [Structural Formula 7] and [Structural Formula 9] Anthracene derivatives characterized.

[Structural formula 1] [Structural formula 2] [Structural formula 4]

[Structural formula 6] [Structural formula 7] [Structural formula 9]
Hydrogen or deuterium may be bonded to the carbon site of the aromatic ring in [Structural Formula 1], [Structural Formula 2], [Structural Formula 4], [Structural Formula 6], [Structural Formula 7] and [Structural Formula 9]. delete The method of claim 1,
The substituent R is selected from a deuterium atom, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 50 aryl group,
Anthracene derivative, characterized in that m is an integer of 0 to 4. The method of claim 1,
The anthracene derivative represented by Formula A is an anthracene derivative, characterized in that it is asymmetric with respect to a straight line consisting _{of L 1} -anthracene-L _{2 .} The method of claim 1,
The compound represented by Formula A is characterized in that any one selected from the group represented by the following [Compound 1] to [Compound 3], [Compound 5], [Compound 6], [Compound 8] to [Compound 21] anthracene derivatives.
<Compound 1><Compound2><Compound3>

<Compound 5><Compound6>

<Compound 8><Compound9>

<Compound 10><Compound11><Compound12>

<Compound 13><Compound14><Compound15>

<Compound 16><Compound17><Compound18>

<Compound 19><Compound20><Compound21>

a first electrode;
a second electrode opposite to the first electrode; and
Including; an organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains at least one compound of any one of claims 1, 2, and 4 to 6, organic light emitting device. 8. The method of claim 7,
The organic layer comprises at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 9. The method of claim 8,
An organic light emitting device, characterized in that the organic layer interposed between the first electrode and the second electrode is a light emitting layer, the light emitting layer consists of a host and a dopant, and a compound included in the organic layer in the organic light emitting device is used as a host. . 9. The method of claim 8,
At least one layer selected from each of the layers is an organic light emitting device, characterized in that it is formed by a deposition process or a solution process. 8. The method of claim 7,
The organic light emitting device may include a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; And, Monochromatic or white flexible lighting device; Organic light emitting device, characterized in that used in any one device selected from.

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