KR102316391B1 - Pyrene derivatives comprising heteroaryl amine groupand organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a pyrene derivative represented by the following [Formula A] and an organic light emitting device comprising the same, wherein the substituents Z, Ar1 to Ar4 and m are the same as defined in the detailed description of the invention.
[Formula A]

Description

Pyrene derivatives comprising heteroarylamine groups and organic light-emitting devices including the same

The present invention relates to a pyrene derivative containing a heteroarylamine group and an organic light emitting device comprising the same, and more particularly, when used as an organic light emitting material, the driving voltage is low, the luminance and luminous efficiency are excellent, and an excellent device with a long lifespan It relates to a pyrene derivative capable of showing characteristics 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 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 When it falls back to the ground state, it lights up. 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, and the like, according to functions. The light emitting material can be classified into a high molecular type and a low molecular type according to 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 a light emitting 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 is shifted 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 a 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. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength may be obtained according to the type of the dopant used.

An organic light emitting device using a pyrene-based derivative to which an amine containing a benzofuran or dibenzofuran group as a substituent is bonded as a prior art related to a dopant compound in such a light emitting layer, Patent Publication No. 10-2010-0097181 (2010.09.02.) is disclosed, and in US Patent Publication No. 5645948 (1997.07.08), an organic light emitting device using a pyrene-based derivative in which a benzoxazole group is directly bonded to pyrene is disclosed.

However, despite the above efforts, the need for developing new organic light emitting materials having superior luminance and luminous efficiency and long lifespan characteristics compared to organic light emitting materials manufactured by the prior art including the prior art is still continuing. It is being demanded.

Laid-Open Patent Publication No. 10-2010-0097181 (2010.09.02)

US Patent Publication No. US 5645948 (July 8, 1997)

Therefore, the first technical task to be achieved by the present invention is a novel organic light emitting diode (OLED) that can be used in the light emitting layer of an organic light emitting diode (OLED), has excellent luminance and luminous efficiency, and exhibits excellent device characteristics with a long lifespan. To provide a light-emitting material.

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

The present invention provides a compound represented by the following [Formula A] in order to achieve the first technical problem.

[Formula A]

In the [Formula A],

The substituent Z is hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, a substituted or unsubstituted and heteroatom N, O, P, Si , Ge, Se, Te, or S having at least one heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or substituted or unsubstituted arylox having 6 to 30 carbon atoms Group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C1C group Any one selected from an arylamine group of 5 to 30, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group , may be connected to each other with adjacent substituents to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O, P, Si, Ge, may be substituted with any one or more heteroatoms selected from Se, Te or S;

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

each carbon atom in the pyrene ring is bonded to a hydrogen atom if not bonded to a nitrogen atom of an amine or a substituent Z;

The substituents Ar ₁ to Ar ₄ are the same or different, and independently of each other, 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 5 It is an aryl group of to 50, or is selected from a heteroaryl group having 2 to 50 carbon atoms, which is substituted or unsubstituted and has any one or more selected from N, O, P, Si, Ge, Se, Te or S as a heteroatom, at least One is a functional group represented by the following [Structural Formula B].

[Structural Formula B]

In Structural Formula B, Y is O or S,

X ₁ to X ₈ are each independently N or CR ₉ , but each CR ₉ is the same as or different from each other, _{and is connected to CR 9} adjacent to each other to form an alicyclic or aromatic monocyclic or polycyclic ring there is,

At least one of X ₁ to X ₈ is N, and R ₉ is the same as Z defined above,

_One of X 1 to X _{8 in} Structural Formula B is a single bond bonded to a nitrogen atom bonded to pyrene of [Formula A].

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

According to the present invention, the compound represented by the [Formula A] has a lower driving voltage, excellent luminance and luminous efficiency, and can show excellent device characteristics for a long life compared to conventional materials, so that it is suitable for a device for manufacturing a full-color display. can be used

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 a pyrene derivative represented by the following [Formula A] as an organic light emitting compound that can be used in a light emitting layer of an organic light emitting device.

[Formula A]

In the [Formula A], the substituent Z is hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C5-C50 aryl group, a substituted or unsubstituted C2-30 An alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 20 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 and heteroatom N, O, P, Si, Ge, Se, Te or S having at least one heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted An aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms , a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, cyano group, nitro group, halogen Any one selected from the group may be connected to each other with adjacent substituents to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O , may be substituted with any one or more heteroatoms selected from P, Si, Ge, Se, Te, or S;

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

each carbon atom in the pyrene ring is bonded to a hydrogen atom if not bonded to a nitrogen atom of an amine or a substituent Z;

The substituents Ar ₁ to Ar ₄ are the same or different, and independently of each other, 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 5 It is an aryl group of to 50, or is selected from a heteroaryl group having 2 to 50 carbon atoms, which is substituted or unsubstituted and has any one or more selected from N, O, P, Si, Ge, Se, Te or S as a heteroatom, at least One is a functional group represented by the following [Structural Formula B].

[Structural Formula B]

In Structural Formula B, Y is O or S,

X ₁ to X ₈ are each independently N or CR ₉ , but each CR ₉ is the same as or different from each other, _{and is connected to CR 9} adjacent to each other to form an alicyclic or aromatic monocyclic or polycyclic ring there is,

At least one of X ₁ to X _{8 is N,}

Wherein R ₉ is the same as Z defined above,

_{One of X 1} to X ₈ in the structural formula B is a single bond bonded to the nitrogen atom bonded to the pyrene of the [Formula A],

'Substitution' in 'substituted or unsubstituted' means deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms. , C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group or C2-C24 heteroarylalkyl group , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl group, means substituted with one or more substituents selected from the group consisting of an aryloxy group having 1 to 24 carbon atoms.

In addition, 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-C24 The range of carbon number of the alkyl group and the aryl group having 6 to 24 carbon atoms means the total number of carbon atoms constituting the alkyl portion or the aryl portion when viewed as unsubstituted without considering the portion in which the substituent is substituted. 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 as a substituent used in the compound of the present invention means an aromatic system consisting of a hydrocarbon including one or more rings, and when the aryl group has a substituent, it is fused with neighboring substituents to form an additional ring can be formed

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 , hydroxy group, nitro group, cyano group, silyl group, 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, 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 a heteroaryl group having 2 to 24 carbon atoms. It may be substituted with a heteroarylalkyl group.

The heteroaryl group as a substituent used in the compound of the present invention includes 1, 2 or 3 heteroatoms selected from N, O, P, Si, Ge, Se, Te, or S, and the remaining ring atoms are carbon atoms having 2 to 24 carbon atoms. of a ring aromatic system, wherein 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, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, and at least one of the alkyl groups A hydrogen atom can be substituted with the same substituent 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.

When driving an organic light emitting device employing the compound represented by Formula A between a pair of electrodes (anode and cathode) in the present invention, the pyrene derivative compound represented by Formula A is a substituent bonded to a nitrogen atom. When the functional group represented by the structural formula B is included, the luminous efficiency of the organic light emitting diode may be increased.

That is, by bonding a heteroarylamine group in which the functional group represented by the structural formula B is bonded to a nitrogen atom in the present invention to pyrene, as a fluorescent dopant It is possible to increase the luminous efficiency of the organic light emitting device.

_{In one embodiment, one or two of Ar 1} to Ar ₄ in Formula A of the present invention is a functional group represented by Structural Formula B, and the amine bonded to the pyrene may be bonded to the 1, 6 position.

In this case, only one or two of _{X 1} to X _{8 in Structural Formula B may be N.}

That is, Structural Formula B may represent a condensed ring in which only one or two carbon atoms in the ring are substituted with nitrogen atoms, except for Y, as an aromatic heterocyclic ring.

_{On the other hand, when Ar 1} to Ar ₄ in the pyrene derivative represented by Formula A of the present invention are not a functional group represented by Formula B, they are preferably the same or different from each other, and have 6 to 14 substituted or unsubstituted carbon atoms. It may be an aryl group, or a substituted or unsubstituted heteroaryl group having 2 to 12 carbon atoms and having at least one selected from N, O, P, Si, Ge, Se, Te, or S as a heteroatom.

Illustratively, Ar ₁ to Ar ₄ may be the same or different from each other, and may be any one selected from the following [Structural Formula 101] to [Structural Formula 208].

[Structural formula 101] [Structural formula 102] [Structural formula 103] [Structural formula 104]

[Structural formula 105] [Structural formula 106] [Structural formula 107]

[Structural formula 108] [Structural formula 109] [Structural formula 110]

[Structural formula 111] [Structural formula 112] [Structural formula 113]

[Structural formula 114] [Structural formula 115] [Structural formula 116]

[Structural formula 117]

[Structural formula 201] [Structural formula 202] [Structural formula 203]

[Structural formula 204] [Structural formula 205] [Structural formula 206]

[Structural formula 207] [Structural formula 208]

where n is an integer from 2 to 9,

When the substituent R is not bonded to the carbon in the aromatic ring or the saturated hydrocarbon ring in [Structural Formula 101] to [Structural Formula 208], hydrogen is bonded,

One of the substituents R in the [Structural Formula 101] to [Structural Formula 208] is a single bond bonded to each nitrogen atom, and the substituent R is the same as Z defined above.

In the pyrene derivative represented by Formula A of the present invention, m is preferably 0 to 2, and the substituent Z is preferably deuterium, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or a substituted or unsubstituted carbon number 1 It may be any one selected from an alkyl group of to 12, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms.

In addition, in the pyrene derivative of the present invention, two amine groups may be the same, and the pyrene derivative may be asymmetric because two amine groups are different from each other.

When the two amine groups are identical, the two amine groups can be prepared by reacting the same type of amine with a halogenated pyrene such as dibromopyrene, and when the two amine groups are different, each different type It can be obtained by sequentially reacting the amines of

In the case of sequentially reacting different amines as described above, the pyrene derivative to which one amine group is bonded as an intermediate may be reacted with a new amine in the next step after purification. When the two amines are different as described above, the obtained pyrene derivative is obtained as an asymmetric compound.

In addition, the pyrene derivative of Formula A of the present invention may be any one selected from the following [Formula 1] to [Formula 96].

[Formula 1] [Formula 2] [Formula 3]

[Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8] [Formula 9]

[Formula 10] [Formula 11] [Formula 12]

[Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17] [Formula 18]

[Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24]

[Formula 25] [Formula 26] [Formula 27]

[Formula 28] [Formula 29] [Formula 30]

[Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36]

[Formula 37] [Formula 38] [Formula 39]

[Formula 40] [Formula 41] [Formula 42]

[Formula 43] [Formula 44] [Formula 45]

[Formula 46] [Formula 47] [Formula 48]

[Formula 49] [Formula 50] [Formula 51]

[Formula 52] [Formula 53] [Formula 54]

[Formula 55] [Formula 56] [Formula 57]

[Formula 58] [Formula 59] [Formula 60]

[Formula 61] [Formula 62] [Formula 63]

[Formula 64] [Formula 65] [Formula 66]

[Formula 67] [Formula 68] [Formula 69]

[Formula 70] [Formula 71] [Formula 72]

[Formula 73] [Formula 74] [Formula 75]

[Formula 76] [Formula 77] [Formula 78]

[Formula 79] [Formula 80] [Formula 81]

[Formula 82] [Formula 83] [Formula 84]

[Formula 85] [Formula 86] [Formula 87]

[Formula 88] [Formula 89] [Formula 90]

[Formula 91] [Formula 92] [Formula 93]

[Formula 94] [Formula 95] [Formula 96]

In addition, the present invention is a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer may provide an organic light emitting device including at least one kind of the pyrene derivative compound in the present invention.

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

In addition, the organic layer containing the organic light emitting 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 this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer may include a host and a dopant, and the pyrene derivative compound of the present invention may be used as a dopant.

Meanwhile, in the present invention, a host material may be used in addition to a dopant for the emission layer. 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.

As a specific example of the present invention, a hole transport layer (HTL, Hole Transport Layer) is further laminated 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 having 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.

Meanwhile, as the material for the electron transport layer in the present invention, a known electron transport material may be used as it functions to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, especially tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, compound 201, compound 202, BCP, and oxadiazole derivatives PBD, BMD, BND, etc. may be used, but are not limited thereto.

TAZ BALQ

<Compound 201> <Compound 202> BCP

In addition, as the electron transport layer used in the present invention, the organometallic compound represented by Formula C may be used alone or in combination with the electron transport layer material.

[Formula C]

In the [Formula C],

Y represents a portion in which any one selected from C, N, O and S is directly bonded to M to form a single bond, and a portion in which any one selected from C, N, O and S forms a coordination bond to M It is a ligand chelated by the single bond and the coordination bond,

wherein M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and OA is a monovalent ligand capable of single or coordinate bonding with M, wherein O is oxygen,

A is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C5 to C50 aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 Any one or more selected from O, N, S and Si as an alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms and a substituted or unsubstituted hetero atom Any one selected from a heteroaryl group having 2 to 50 carbon atoms,

When M is one metal selected from alkali metals, m = 1, n = 0,

When M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,

When M is boron or aluminum, m = any one of 1 to 3, n is any one of 0 to 2, and satisfies m + n = 3;

'Substitution' in the 'substituted or unsubstituted' is deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a hetero arylamino group, an alkylsilyl group, an arylsilyl group, It means substituted with one or more substituents selected from the group consisting of an aryloxy group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, each Y is the same or different, and may be any one independently selected from the following [Structural Formula C1] to [Structural Formula C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the [Structural Formula C1] to [Structural Formula C39],

R is the same as or different from each other, and each independently represents hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted A C 3 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 30 alkoxy group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or An unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 arylsilyl group It is selected from the group, and may be connected with an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

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 particular limitation, for example, LiF, NaCl, CsF, Li ₂ O, materials such as 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 possible to further form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer may be further formed.

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 .

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. However, the present invention is not necessarily limited thereto.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, 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), etc. can be used. However, the present invention is not necessarily limited thereto.

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, etc. 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, the light emitting layer may be formed of a host and a dopant.

In addition, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 Å.

In this case, the host used in the light emitting layer may be a compound represented by the following Chemical Formulas 1A to 1D.

[Formula 1A]

In Formula 1A,

The Ar _{7 ,} Ar ₈ and Ar ₉ are the same as or different from each other and each independently represent a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ a heteroaromatic linking group;

said R ₂₁ to R ₃₀ are the same as or different from each other and are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group or a salt thereof, a 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 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 of (alkyl)amino group, di(substituted or unsubstituted C1-C60 alkyl)amino group, or (substituted or unsubstituted C6-C60 aryl)amino group, di(substituted or unsubstituted C6-C60 Aryl) may be selected from an amino group, a substituted or unsubstituted C1-C40 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, germanium, phosphorus, and boron, and each substituent is adjacent to each other. can form a condensed ring with the group;

wherein e, f and g are the same as or different from each other and each independently 0 or an integer of 1 to 4;

The two sites marked with * of the anthracene may be the same or different from each other, and may each independently combine with the P or Q structure to constitute an anthracene-based derivative selected from the following Chemical Formulas 1Aa-1 to 1Aa-3.

[Formula 1Aa-1] [Formula 1Aa-2] [Formula 1Aa-3]

Here, 'substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 Alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group or C2-C24 hetero Arylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylamino group It means substituted with one or more substituents selected from the group consisting of an arylsilyl group and an aryloxy group having 1 to 24 carbon atoms.

[Formula 1B]

In Formula 1B,

Ar ₁₇ to Ar ₂₀ are the same as or different from each other and each independently consists of the same substituents as defined _{for Ar 7} to Ar _{8 in Formula 1A, and R 60} to R ₆₃ are R ₂₁ to R ₃₀ in Formula 1A and the same substituents as

The w and ww are the same as or different from each other, the x and xx are the same as or different from each other, and the values of w+ww and x+xx are the same or different from each other and are each independently an integer of 0 to 3. In addition, the y and yy are the same as or different from each other, the z and zz are the same or different from each other, the y+yy to z+zz values are 2 or less, and each is an integer of 0 to 2.

[Formula 1C]

In Formula 1C,

Ar ₂₁ to Ar ₂₄ are the same as or different from each other and each independently consist of the same substituents as defined in _{Ar 7} to Ar _{8 of Formula 1A, and R 64} to R _{67 are R 21} to R ₃₀ of Formula 1A It consists of the same substituents as defined.

In addition, the ee to hh are the same as or different from each other and each independently an integer of 1 to 4, and ii to ll are the same or different from each other and each independently an integer of 0 to 4.

[Formula 1D]

In Formula 1D,

wherein Ar ₂₅ to Ar ₂₇ are the same as or different from each other and each independently consist of the same substituents as defined in _{Ar 7} to Ar _{8 of Formula 1A, and R 68} to R ₇₃ are the same as or different from each other and each independently represent the above formula It consists of the same substituents as defined for R ₂₁ to R ₃₀ of 1A, and each substituent may form a saturated or unsaturated cyclic structure with adjacent ones. In addition, the mm to ss are the same as or different from each other and are each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group represented by the following [Host 1] to [Host 56], but is not limited thereto.

[Host1] [Host2] [Host3] [Host4]

[Host5] [Host6] [Host7] [Host8]

[Host9] [Host10] [Host11] [Host12]

[Host 13] [Host 14] [Host 15] [Host 16]

[Host 17] [Host 18] [Host 19] [Host 20]

[Host 21] [Host 22] [Host 23] [Host 24]

[Host 25] [Host 26] [Host 27] [Host 28]

[Host 29] [Host 30] [Host 31] [Host 32]

[Host 33] [Host 34] [Host 35] [Host 36]

[Host 37] [Host 38] [Host 39] [Host 40]

[Host 41] [Host 42] [Host 43] [Host 44]

[Host 45] [Host 46] [Host 47] [Host 48]

[Host 49] [Host 50] [Host 51] [Host 52]

[Host 53] [Host 54] [Host 55] [Host 56]

In addition, the light emitting layer may further include various hosts and various dopant materials in addition to the dopant and host.

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, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer is a single molecule It may be formed by a deposition method or a solution process. 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 methods 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.

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.

(Example)

Synthesis Example 1: Synthesis of Formula 5

Synthesis example 1-(1): Synthesis of [Intermediate 1-a]

According to Scheme 1 below, [Intermediate 1-a] was synthesized.

<Scheme 1>

[Intermediate 1-a]

2,6-dibromophenol (50 g, 0.198 mol) and anhydrous tetrahydrofuran (250 ml) were placed in a well-dried 500ml three-neck round bottom flask. The temperature was lowered to 0 °C, diisopropylethylamine (70.2 ml, 0.403 mol) was added, and methoxymethyl chloride (22.61 ml, 0.298 mol) was slowly added thereto. After stirring at 0° C. for 2 hours, extraction was performed, and separation by column chromatography was performed to obtain [Intermediate 1-a] as a transparent oil. (54.6 g, yield 93%)

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

[Intermediate 1-b] was synthesized according to Scheme 2 below.

<Scheme 2>

[Intermediate 1-b]

[Intermediate 1-a] (54.6 g, 0.184 mol) and anhydrous tetrahydrofuran (380 ml) were placed in a well-dried 1 L three-neck round bottom flask. The temperature was lowered to -78 °C and 1.6 M n-butyllithium (127 ml, 0.203 mol) was slowly added thereto. After stirring at -78 °C for 1 hour, trimethylborate (101 ml, 0.830 mol) was added at a time, and the temperature was raised to room temperature and stirred for 10 hours. Saturated ammonium chloride solution (200 ml) was added, and the reaction was terminated by stirring for 1 hour, followed by extraction and concentration under reduced pressure to obtain [Intermediate 1-b]. (30 g, yield 80%)

Synthesis example 1-(3): Synthesis of [Intermediate 1-c]

According to Scheme 3 below, [Intermediate 1-c] was synthesized.

<Scheme 3>

[Intermediate 1-b] [Intermediate 1-c]

2-fluoro-3-iodopyridine (21.5 g, 0.096 mol), [Intermediate 1-b] (30 g, 0.116 mol), 2% tetrakistriphenylphosphine palladium (2.23 g) in a 500 ml three-necked round-bottom flask , 0.002 mol), 3 M disodium carbonate (100 ml), and tetrahydrofuran (200 ml) were added. After stirring for 16 hours, refluxing, extraction, concentration under reduced pressure, and separation by column chromatography to obtain [Intermediate 1-c]. (14.5 g, yield 56%)

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

[Intermediate 1-d] was synthesized according to Scheme 4 below.

<Scheme 4>

[Intermediate 1-c] [Intermediate 1-d]

[Intermediate 1-c] (14.5 g, 0.054 mol), potassium carbonate (15 g, 0.108 mol), and tetrahydrofuran (150 ml) were placed in a 500ml three-neck round bottom flask. After stirring and refluxing for 12 hours, the reaction was terminated. After extraction by concentration under reduced pressure, the resultant was separated by column chromatography to obtain [Intermediate 1-d]. (13 g, yield 97%)

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

[Intermediate 1-e] was synthesized according to Scheme 5 below.

<Scheme 5>

[Intermediate 1-d] [Intermediate 1-e]

[Intermediate 1-d] (4.4 g, 0.018 mol), 2-aminobiphenyl (3 g, 0.018 mol), tris(dibenzylideneacetone)dipalladium(0) (0.32 g, 0.355) in a 100ml three-neck round bottom flask mmol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (0.44 g, 0.709 mmol), sodium tert-butoxide (3.41 g, 0.035 mol), toluene (60 ml) put After stirring and refluxing for 3 hours, the reaction was terminated. After extraction, [Intermediate 1-e] was obtained by column chromatography. (4.7 g, yield 67%)

Synthesis Example 1-(6): Synthesis of [Formula 5]

[Formula 5] was synthesized according to Scheme 6 below.

<Scheme 6>

[Intermediate 1-e] [Formula 5]

[Intermediate 1-e] (4.7 g, 0.014 mol), 1,6-dibromopyrene (2.3 g, 0.006 mol), tris(dibenzylideneacetone)dipalladium(0) (0.26) in a 100ml three-neck round bottom flask g, 0.279 mmol), 1 M tritertiarybutylphosphine (0.56 ml, 0.559 mmol), sodium tert-butoxide (2.69 g, 0.028 mol), and toluene (50 ml) were added. After stirring and refluxing for 2 hours, the reaction was terminated. It was extracted and recrystallized from chlorobenzene to obtain [Formula 5]. (3.5 g, yield 57%)

MS (MALDI-TOF) m/z :870.3 [M ⁺ ]

Synthesis Example 2: Synthesis of Formula 41

Synthesis Example 2-(1): Synthesis of [Intermediate 2-a]

[Intermediate 2-a] was synthesized according to Scheme 7 below.

<Scheme 7>

[Intermediate 2-a]

In Synthesis Example 1-(1), 2,6-dibromo-4-tert-butylphenol (144 g, 0.468 mol) was used instead of 2,6-dibromophenol. Intermediate 2-a] was obtained. (163 g, yield 99%)

Synthesis Example 2-(2): Synthesis of [Intermediate 2-b]

[Intermediate 2-b] was synthesized according to Scheme 8 below.

<Scheme 8>

[Intermediate 2-b]

[Intermediate 2-b] was obtained in the same manner except that [Intermediate 2-a] (100 g, 0.284 mol) was used instead of [Intermediate 1-a] in Synthesis Example 1-(2). (75 g, yield 83%)

Synthesis Example 2-(3): Synthesis of [Intermediate 2-c]

[Intermediate 2-c] was synthesized according to Scheme 9 below.

<Scheme 9>

[Intermediate 2-b] [Intermediate 2-c]

[Intermediate 2-c] was obtained in the same manner as in Synthesis Example 1-(3), except that [Intermediate 2-b] was used instead of [Intermediate 1-b]. (46 g, yield 60%)

Synthesis Example 2-(4): Synthesis of [Intermediate 2-d]

[Intermediate 2-d] was synthesized according to Scheme 10 below.

<Scheme 10>

[Intermediate 2-c] [Intermediate 2-d]

[Intermediate 2-d] was obtained in the same manner as in Synthesis Example 1-(4), except that [Intermediate 2-c] (46 g, 0.142 mol) was used instead of [Intermediate 1-c]. (40 g, yield 93%)

Synthesis Example 2-(5): Synthesis of [Intermediate 2-e]

[Intermediate 2-e] was synthesized according to Scheme 11 below.

<Scheme 11>

[Intermediate 2-d] [Intermediate 2-e]

[Intermediate 2-e] was obtained in the same manner as in Synthesis Example 1-(5), except that [Intermediate 2-d] (6.8 g, 0.022 mol) was used instead of [Intermediate 1-d]. (7.4 g, yield 84%)

Synthesis of Synthesis Example 2-(6): [Formula 41]

[Formula 41] was synthesized according to Scheme 12 below.

<Scheme 12>

[Intermediate 2-e] [Formula 41]

[Formula 41] was obtained by the same experiment except that [Intermediate 2-e] (5.4 g, 0.014 mol) was used instead of [Intermediate 1-e] in Synthesis Example 1-(6). (3.2 g, yield 47%)

MS (MALDI-TOF) m/z :982.42 [M ⁺ ]

Synthesis Example 3: Synthesis of Chemical Formula 73

Synthesis Example 3-(1): Synthesis of [Intermediate 3-a]

[Intermediate 3-a] was synthesized according to Scheme 13 below.

<Scheme 13>

[Intermediate 1-e] [Intermediate 3-a]

[Intermediate 1-e] (5.4 g, 0.016 mol), 1,6-dibromopyrene (8.7 g, 0.024 mol), tris(dibenzylideneacetone)dipalladium(0) (0.29) in a 100ml three-neck round bottom flask g, 0.321 mmol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (0.4 g, 0.642 mmol), sodium tert-butoxide (2.16 g, 0.022 mol), toluene (50 ml) was added. After stirring and refluxing for 2 hours, the reaction was terminated. After extraction, it was separated by column chromatography to obtain [Intermediate 3-a]. (8.2 g, yield 83%)

Synthesis Example 3-(2): Synthesis of [Formula 73]

[Formula 73] was synthesized according to Scheme 14 below.

<Scheme 14>

[Intermediate 2-e] [Intermediate 3-a] [Formula 73]

[Intermediate 2-e] (8 g, 0.02 mol), [Intermediate 3-a] (11.3 g, 0.018 mol), tris(dibenzylideneacetone)dipalladium(0) (0.37 g, 0.408 mmol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (0.51 g, 0.815 mmol), sodium tert-butoxide (2.74 g, 0.029 mol), toluene (80 ml) put in After stirring and refluxing for 4 hours, the reaction was terminated. It was extracted and recrystallized from chlorobenzene to obtain [Formula 73]. (10.2 g, yield 54%)

MS (MALDI-TOF) m/z :926.36 [M ⁺ ]

Synthesis Example 4: Synthesis of Formula 79

Synthesis Example 4-(1): Synthesis of [Intermediate 4-a]

[Intermediate 4-a] was synthesized according to Scheme 15 below.

<Scheme 15>

[Intermediate 4-a]

N-hydroxy-2-thiopyridone (10 g, 0.079 mol) and dichloromethane (100 ml) were added to a 250 ml three-neck round bottom flask wrapped with silver foil, and the temperature was lowered to 0 °C. Pyridine (6.4 ml, 0.083 mol) and acetyl chloride (5.6 ml, 0.065 mol) were added and stirred for 2 hours. After extraction, it was placed in a round-bottom flask wrapped with silver foil and concentrated under reduced pressure at less than 20 °C. Recrystallization from dichloromethane and heptane gave [Intermediate 4-a]. (12 g, yield 90%)

Synthesis Example 4-(2): Synthesis of [Intermediate 4-b]

[Intermediate 4-b] was synthesized according to Scheme 16 below.

<Scheme 16>

[Intermediate 4-a] [Intermediate 4-b]

[Intermediate 4-a] (12 g, 0.071 mol), isopentylnitrite (24.9 g, 0.213 mol), and dichloromethane (300 ml) were placed in a 1 L three-necked round-bottom flask wrapped in silver foil, and stirred and refluxed while stirring, Anthranilic acid (9.7 g, 0.071 mol) dissolved in acetone (150 ml) was slowly added for 60 minutes. After stirring and refluxing for 3 hours, the temperature was lowered to room temperature, and the solvent was concentrated under reduced pressure. It was separated by column chromatography to obtain [Intermediate 4-b]. (7.5 g, yield 57%)

Synthesis Example 4-(3): Synthesis of [Intermediate 4-c]

[Intermediate 4-c] was synthesized according to Scheme 17 below.

<Scheme 17>

[Intermediate 4-b] [Intermediate 4-c]

[Intermediate 4-b] (20 g, 0.108 mol) and dichloromethane (100 ml) were put in a 300 ml three-necked round-bottom flask, and N-bromosuccinimide (19.2 g, 0.108 mol) was slowly added thereto at room temperature. Stirred for 3 hours. After extraction, the organic layer was concentrated under reduced pressure, separated by column chromatography, and recrystallized from dichloromethane and heptane to obtain [Intermediate 4-c]. (7.2 g, yield 25%)

Synthesis Example 4-(4): Synthesis of [Intermediate 4-d]

[Intermediate 4-d] was synthesized according to Scheme 18 below.

<Scheme 18>

[Intermediate 4-d]

2-amino-3-bromo-5-methylpyridine (13 g, 0.07 mol), phenylboronic acid (10.2 g, 0.083 mol), tetrakistriphenylphosphine palladium (1.6 g) in a 300 ml three-necked round-bottom flask , 1.39 mmol), 2 M aqueous potassium carbonate solution (70 ml), and tetrahydrofuran (140 ml) were added, followed by stirring and refluxing for 6 hours. After extraction, the organic layer was concentrated under reduced pressure and recrystallized from acetonitrile to obtain [Intermediate 4-d]. (11 g, yield 86%)

Synthesis Example 4-(5): Synthesis of [Intermediate 4-e]

[Intermediate 4-e] was synthesized according to Scheme 19 below.

<Scheme 19>

[Intermediate 4-c] [Intermediate 4-d] [Intermediate 4-e]

[Intermediate 4-c] (7.2 g, 0.027 mol) was used instead of [Intermediate 1-d] in Synthesis Example 1-(5), and [Intermediate 4-d] (5.0 g, 0.027 mol) was used instead of 2-aminobiphenyl ), [Intermediate 4-e] (9.2 g, yield 92%) was obtained in the same manner except that it was used.

Synthesis Example 4-(6): Synthesis of [Formula 79]

[Formula 79] was synthesized according to Scheme 20 below.

<Scheme 20>

[Intermediate 4-e] [Formula 79]

In Synthesis Example 1-(6), [Intermediate 4-e] instead of [Intermediate 1-e], 1,6-dibromo-2,7-dimethylpyrene was used instead of 1,6-dibromopyrene Except for the same experiment, [Formula 79] was obtained. (11 g, yield 46%)

MS (MALDI-TOF) m/z :960.31 [M ⁺ ]

Synthesis Example 5: Synthesis of Formula 86

Synthesis Example 5-(1): Synthesis of [Intermediate 5-a]

[Intermediate 5-a] was synthesized according to Scheme 21 below.

<Scheme 21>

[Intermediate 1-b] [Intermediate 5-a]

[Intermediate 5-a] was obtained in the same manner as in Synthesis Example 1-(3), except that 3-fluoro-4-iodo pyridine was used instead of 2-fluoro-3-iodo pyridine. (12 g, yield 50%)

Synthesis Example 5-(2): Synthesis of [Intermediate 5-b]

[Intermediate 5-b] was synthesized according to Scheme 22 below.

<Scheme 22>

[Intermediate 5-a] [Intermediate 5-b]

[Intermediate 5-b] was obtained in the same manner as in Synthesis Example 1-(4), except that [Intermediate 5-a] was used instead of [Intermediate 1-c]. (10.5 g, yield 95%)

Synthesis Example 5-(3): Synthesis of [Intermediate 5-c]

[Intermediate 5-c] was synthesized according to Scheme 23 below.

<Scheme 23>

[Intermediate 5-b] [Intermediate 5-c]

[Intermediate 5-c] was obtained in the same manner as in Synthesis Example 1-(5), except that [Intermediate 5-b] was used instead of [Intermediate 1-d]. (12.3 g, yield 86%)

Synthesis of Synthesis Example 5-(4): [Formula 86]

[Formula 86] was synthesized according to Scheme 24 below.

<Scheme 24>

[Intermediate 5-c] [Formula 86]

In Synthesis Example 1-(6), [Formula 86] was obtained in the same manner except that [Intermediate 5-c] was used instead of [Intermediate 1-e]. (8.7 g, yield 55%)

MS (MALDI-TOF) m/z :870.3 [M ⁺ ]

Examples 1 to 7: Preparation of organic light emitting device

After patterning so that the light emitting area of the ITO glass is 2mm × 2mm in size, it was washed. After the ITO glass was mounted in a vacuum chamber, the base pressure was set to 1×10 ^-7 torr, and then a film was formed on the ITO in the order of DNTPD (700 Å) and α-NPD (300 Å), [BH1] and Table 1 A film was formed by mixing 3 wt% of the compound according to the present invention described in (250 _{Å), and then Alq 3} (350 Å), LiF (5 Å), and Al (1000 Å) were formed into a film in this order to prepare an organic light-emitting device. The emission characteristics of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [α-NPD]

[BH1] [Alq ₃ ]

Comparative Examples 1 and 2

An organic light emitting device was manufactured in the same manner except that [BD1] and [BD2] were used instead of the compounds used in Examples 1 to 7, and the light emitting characteristic of the organic light emitting device was measured at 0.4 mA. The structures of [BD1] and [BD2] are as follows.

[BD1] [BD2]

For the organic electroluminescent devices manufactured according to Examples 1 to 7 and Comparative Examples 1 to 2, voltage, current, luminance, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T97 means the time it takes for the luminance to decrease to 97% compared to the initial luminance.

Voltage current density
( mA /cm ² ) luminance ( CD /m ² ) CIEx CIEy T97 Example 1
[Formula 5] 3.8 10 718 0.135 0.111 32 Example 2
[Formula 11] 3.7 10 620 0.138 0.125 33 Example 3
[Formula 22] 3.8 10 600 0.132 0.116 30 Example 4
[Formula 33] 3.5 10 650 0.132 0.110 40 Example 5
[Formula 41] 3.7 10 742 0.131 0.130 45 Example 6
[Formula 73] 3.8 10 742 0.133 0.120 40 Example 7
[Formula 79] 3.7 10 742 0.132 0.111 48 Example 8
[Formula 81] 3.7 10 720 0.135 0.124 40 Example 9
[Formula 86] 3.8 10 730 0.132 0.132 52 Example 10
[Formula 90] 3.7 10 720 0.133 0.133 60 Comparative Example 1
[BD1] 4.3 10 515 0.143 0.118 20 Comparative Example 2
[BD2] 4.3 10 550 0.141 0.117 22

As shown in Table 1, the pyrene derivative according to the present invention has much superior luminance and luminous efficiency, lower driving voltage, and long lifespan compared to the case of using the compounds of Comparative Examples 1 and 2 according to the prior art. can be shown, indicating high application potential as an organic light emitting device.

Claims (13)

A pyrene derivative represented by the following [Formula A].
[Formula A]

In the [Formula A], the substituent Z is hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-30 A cycloalkyl group, a substituted or unsubstituted heteroaryl group having at least one selected from N, O, P, Si, and S as a heteroatom, a heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a halogen Any one selected from the group may be connected to each other with adjacent substituents to form an alicyclic, aromatic monocyclic or polycyclic ring,
m is an integer from 1 to 8, but when m is 2 or more, each Z is the same as or different from each other,
each carbon atom in the pyrene ring is bonded to a hydrogen atom if not bonded to a nitrogen atom of an amine or a substituent Z;
The substituents Ar ₁ to Ar ₄ are the same or different, and independently of each other, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or a substituted or unsubstituted hetero atom selected from N, O, P, Si or S having at least either one being odd heteroaryl having 2 to 12 carbon atoms that is, a functional group wherein the dog Ar 1 or 2 of from ₁ to Ar ₄ is represented by the structural formula B,
[Structural Formula B]

In Structural Formula B, Y is O or S,
X ₁ to X ₈ are each independently N or CR ₉ , but each CR ₉ is the same as or different from each other, _{and is connected to CR 9} adjacent to each other to form an alicyclic or aromatic monocyclic or polycyclic ring there is,
Only one or two of the X ₁ to X _{8 is N,}
Wherein R ₉ is the same as Z defined above,
_One of X 1 to X _{8 in} the structural formula B is a single bond bonded to the nitrogen atom bonded to the pyrene of the [Formula A],
'Substitution' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C6-C24 aryl group, carbon number 6-24 arylalkyl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylsilyl group, C6-C24 arylsilyl group group, means substituted with one or more substituents selected from the group consisting of an aryloxy group having 6 to 24 carbon atoms. The method of claim 1,
The amine bonded to the pyrene is a pyrene derivative, characterized in that bonded to the 1, 6 position. delete 3. The method of claim 2,
When Ar _{1 To} Ar ₄ is not a functional group represented by Structural Formula B, they are the same or different, respectively, and a substituted or unsubstituted C 6 to C 14 aryl group, or a substituted or unsubstituted and heteroatom N, O, P A pyrene derivative, characterized in that it is a heteroaryl group having 2 to 12 carbon atoms and having at least one selected from Si, S. The method of claim 1,
Wherein m is 1 to 2,
Substituent Z is deuterium, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms pyrene derivatives. 6. The method of any one of claims 1, 2, 4 and 5,
The pyrene derivative is a pyrene derivative, characterized in that two amine groups are the same. 6. The method of any one of claims 1, 2, 4 and 5,
The pyrene derivative is a pyrene derivative, characterized in that the two amine groups are different from each other and thus asymmetric. The method of claim 1,
The following [Formula 1] to [Formula 8], [Formula 10] to [Formula 17], [Formula 19] to [Formula 26], [Formula 28] to [Formula 35], [Formula 37] to [Formula 44] , [Formula 46] to [Formula 53], [Formula 54] to [Formula 62], [Formula 64] to [Formula 71], [Formula 73] to [Formula 82], [Formula 84] to [Formula 96] Any one pyrene derivative selected from.
[Formula 1] [Formula 2] [Formula 3]

[Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8]

[Formula 10] [Formula 11] [Formula 12]

[Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17]

[Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 28] [Formula 29] [Formula 30]

[Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35]

[Formula 37] [Formula 38] [Formula 39]

[Formula 40] [Formula 41] [Formula 42]

[Formula 43] [Formula 44]

[Formula 46] [Formula 47] [Formula 48]

[Formula 49] [Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Formula 55] [Formula 56] [Formula 57]

[Formula 58] [Formula 59] [Formula 60]

[Formula 61] [Formula 62]

[Formula 64] [Formula 65] [Formula 66]

[Formula 67] [Formula 68] [Formula 69]

[Formula 70] [Formula 71]

[Formula 73] [Formula 74] [Formula 75]

[Formula 76] [Formula 77] [Formula 78]

[Formula 79] [Formula 80] [Formula 81]

[Formula 82] [Formula 84]

[Formula 85] [Formula 86] [Formula 87]

[Formula 88] [Formula 89] [Formula 90]

[Formula 91] [Formula 92] [Formula 93]

[Formula 94] [Formula 95] [Formula 96]

a first electrode;
a second electrode opposite the first electrode; and
An organic layer interposed between the first electrode and the second electrode, wherein the organic layer is a pyrene derivative compound of any one of claims 1, 2, 4, 5 and 8 An organic light emitting device, including one or more kinds. 10. The method of claim 9,
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. 10. The method of claim 9,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer comprises a host and a dopant, and the organic light emitting compound is used as a dopant. 11. The method of claim 10,
One or more layers selected from the respective layers are formed by a deposition process or a solution process. 10. The method of claim 9,
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 selected from.

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