KR20190134356A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound, which is represented by chemical formulas I to IV, has excellent solubility in an organic solvent to perform a solution process when a device is manufactured, and improves light emission properties such as low-voltage driving, light emitting efficiency, and long lifespan when being employed to a device, and to an organic light emitting device employing the same.

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light-emitting compound, and more particularly, it is excellent in solubility in an organic solvent to enable a solution process in manufacturing a device, and when employed in the device to improve the light emission characteristics such as low voltage driving, luminous efficiency and long life A light emitting compound and an organic light emitting device employing the same.

Recently, the organic light emitting device capable of low-voltage driving by self-emission type has better viewing angle, contrast ratio, etc., does not need backlight, light weight and thinness, is advantageous in terms of power consumption, and color reproduction range compared to the liquid crystal display which is the mainstream of flat panel display devices. It is widely attracting attention as a next generation display device.

An organic light emitting device emits light when electrons and holes are paired and extinguished when electric charge is injected into the organic light emitting layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode). In addition to the device can be formed on the substrate, it is possible to drive at a lower voltage of 10V or less than the plasma display panel or the inorganic light emitting display, has the advantage of relatively low power consumption and excellent color. In addition, since the organic light emitting device can display three colors of green, blue, and red, it has been attracting much attention as a next-generation rich color display device.

The organic light emitting device divides the process for emitting light, that is, charge injection, charge transport, photo-exciter formation, and light generation by using different organic layers. Accordingly, an organic light emitting device having a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like divided between the anode and the cathode and having more layers is used, and the organic light emitting device has the aforementioned characteristics. In order to exert, the material that forms the organic layer in the device must be preceded by a stable and efficient material such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, an electron blocking material, etc. The development of an efficient organic material layer for an organic light emitting device has not been made sufficiently.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, it is necessary to first support the material constituting the organic material layer in the device, such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. by a stable and efficient material. However, the development of a stable and efficient organic material layer for an organic electric device has not yet been made sufficiently, and therefore, development of new materials is continuously required.

In addition, large area display manufacturing by the solution process is a necessary reality at the present time when the large area of the organic electric element is required. Although much research has been conducted on polymer materials as a material for the solution process, a solution process without crosslinking damages the lower layer by eroding the lower layer due to the solvent used in forming the upper layer. This brings about a problem of deterioration of device characteristics and process yield.

In the formation of the upper layer, crosslinking is essential to prevent erosion of the lower layer. Thus, crosslinking is possible, having high solubility in organic solvents before crosslinking and low solubility in organic solvents after crosslinking. Compounds should be used.

Accordingly, the present invention provides an organic light emitting compound which is excellent in solubility in organic solvents and can improve the light emitting characteristics of a device for manufacturing a large area display by a solution process. An object is to provide an organic light emitting device capable of stably implementing characteristics such as long life.

In order to solve the above problems, the present invention provides an organic light emitting compound which is represented by [Formula I] to [Formula IV] and has a crosslinking property to which a solution process can be applied.

[Formula I]

[Formula II]

[Formula III]

[Formula IV]

The structures of [Formula I] to [Formula IV] and L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , Ar ₃ And A ₁ to A ₅ will be described later.

The organic light emitting compound according to the present invention has an excellent solubility in organic solvents to enable the implementation of a large-area display device by a solution process, by using the organic light emitting device with improved light emission characteristics such as low voltage drive, luminous efficiency and long life Implementation of is possible.

1 is a representative view showing the structure of an organic light emitting compound according to the present invention.

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

One aspect of the present invention relates to an organic light emitting compound that has excellent solubility in organic solvents, thereby enabling a solution process in device fabrication, and improving light emission characteristics such as low voltage driving, light emission efficiency, and long life when employed in devices.

[Formula I]

[Formula II]

[Formula III]

[Formula IV]

In [Formula I] to [Formula IV],

L ₁ , L ₂ and L ₃ are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted fluorene And l, n and m are each an integer of 1 to 3, and when L, n and m are each 2 or more, a plurality of L ₁ , L ₂ and L ₃ are the same as or different from each other.

Ar ₁ , Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted hetero atom having 2 to 30 carbon atoms. It is selected from an aryl group, o, p and q are each an integer of 1 to 3, when o, p and q are each 2 or more, a plurality of Ar ₁ to Ar ₃ are the same or different from each other.

Meanwhile, Ar ₁ , Ar _2, and Ar ₃ may be bonded to each other or connected to adjacent substituents to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon source of the formed alicyclic or aromatic monocyclic or polycyclic ring Can be substituted with any one or more heteroatoms selected from N, S and O.

A ₁ to A ₅ are each independently hydrogen, deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, carbonyl group, ether group, silane group, siloxane group, substituted or unsubstituted C 1-20 Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms , Substituted or unsubstituted fluorenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms Substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or Unsubstituted C7-30 arylalkyl group, substituted or unsubstituted C2-30 alkenyloxyl group, substituted or unsubstituted C8-30 alkenylaryl group, substituted or unsubstituted C7-30 Arylalkoxy group, a substituted or unsubstituted arylalkenyl group having 8 to 30 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms.

The term 'substituted', L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , Ar ₃ And A ₁ to A ₅ are each further substituted with at least one substituent, wherein the at least one substituent is deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, carbonyl group, ether group, Silane group, siloxane group, C1-C20 alkyl group, C3-C20 cycloalkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C1-C20 halogenated alkyl group, fluorenyl group , Aryl group having 6 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, aryl having 6 to 30 carbon atoms Silyl group, arylalkyl group having 7 to 30 carbon atoms, alkenyloxyl group having 2 to 30 carbon atoms, alkenylaryl group having 8 to 30 carbon atoms, arylalkoxy group having 7 to 30 carbon atoms, arylalkene having 8 to 30 carbon atoms It is selected from an alkoxycarbonyl group and a group having 2 to 20 carbon atoms.

In addition, the compounds of Formula Ⅰ] to [formula Ⅳ] according to the present invention as having a cross-linking property, the Formula Ⅰ] from A ₁ to A _3, at least one, said Formula Ⅱ] from A ₁ and A of At least one of ₄ , at least one of A ₁ to A ₃ and A ₅ in [Formula III], at least one of A ₁ , A ₄ and A ₅ in [Formula IV], respectively, (vinyl), acryl Acrylloyl, methacryloyl, cyclic ethers, siloxanes, styrenes, trifluorovinyl ethers, benzocyclobutenes It is characterized in that it comprises at least one crosslinking group selected from cinnamates (cinnamates), chalcones (chalcones), and oxetane (oxetane).

More specifically at least one of A ₁ to A ₃ in [Formula I], at least one of A ₁ and A ₄ in [Formula II], at least one of A ₁ to A ₃ and A ₅ in [Formula III] At least one of A ₁ , A ₄ and A ₅ in [Formula IV] is characterized in that it includes a substituent structure of any one structure selected from the following [Formula 1] or two or more selected substituents connected to each other. .

[Formula 1]

In addition, in the following structures introduced into the skeleton of [Formula I] to [Formula IV] according to the present invention, at least one of Ar ₁ and Ar ₂ is characterized in that any one selected from the following [formula 2]

[Formula 2]

In the present invention, examples of the substituents will be described in detail below, but is not limited thereto.

In the present invention, the alkyl group may be linear or branched chain, specific examples are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group , sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group and the like, but are not limited thereto. In addition, "cycloalkyl" means alkyl forming a ring.

The alkoxy group, which is a substituent used in the present invention, means an alkyl group to which an oxygen radical is attached, and specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy and hexyl jade. And at least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

"Alkenyl group" or "alkynyl group" used in the present invention, unless otherwise specified, each has a double bond or a triple bond, and includes a straight chain or branched chain group, but is not limited thereto, and specific examples of the alkenyl group Examples include linear or branched alkenyl groups, 3-pentenyl group, 4-hexenyl group, 5-heptenyl group, 4-methyl-3-pentenyl group, 2,4-dimethyl-pentenyl group, 6-methyl -5-heptenyl group, 2,6-dimethyl-5-heptenyl group, etc. are mentioned.

In the present invention, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group and the like. However, the present invention is not limited thereto.

Specific examples of the halogen group which is a substituent used in the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

In the present invention, the aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene group, and the like, and examples of the polycyclic aryl group include naphthyl group and anthracenyl group. , Phenanthrenyl group, pyrenyl group, peryllenyl group, tetrasenyl group, chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention It is not limited only to these examples.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N or S as a hetero atom, and examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group and oxa Diazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl Group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene Group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, etc. There is, but is not limited to these.

In the present invention, the aryl group in the arylthio group, the arylamine group, and the arylsilyl group is the same as the examples of the aryl group described above.

In the present invention, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

Specific examples of the arylamine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenyl Amine groups, 9-methyl-anthracenylamine groups, diphenyl amine groups, phenyl naphthyl amine groups, ditolyl amine groups, phenyl tolyl amine groups, carbazole groups, and triphenyl amine groups, but are not limited thereto.

In the present invention, the carbonyl group is represented by -COR ', wherein R' is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or a combination thereof.

In the present invention, the ether group is represented by -RO-R ', wherein R or R' are each independently hydrogen, an alkyl group, an aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group, an alkynyl group, or a It is a combination.

The organic light emitting compound according to the present invention represented by the above [Formula I] to [Formula IV] can be used as the organic material layer of the organic light emitting device formed by the solution process due to its structural specificity.

Preferred specific examples of the organic light emitting compound represented by [Formula I] to [Formula IV] according to the present invention include the following compounds, but are not limited thereto.

The present invention relates to an organic light emitting device comprising a compound according to [Formula I] to [Formula IV], an organic light emitting device according to an embodiment includes a first electrode and a second electrode and an organic material layer disposed therebetween. It may be made of a structure that can be prepared using conventional device manufacturing methods and materials, except that the organic light emitting compound according to the present invention is used in the organic material layer of the device.

The organic material layer of the organic light emitting device according to the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. However, the present invention is not limited thereto, and may include fewer organic layers.

The organic material layer structure and the like of the preferred organic light emitting device according to the present invention will be described in more detail in the following examples.

In addition, the organic light emitting device according to the present invention using a metal vapor deposition (PVD) method such as sputtering (e-beam evaporation), metal or conductive metal oxides or alloys thereof on the substrate It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer is a solution process or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor) using various polymer materials It can be produced in fewer layers by methods such as a blading process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

As the cathode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) Metal oxides, combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT) Conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof, multilayer such as LiF / Al or LiO ₂ / Al. Structural materials and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

As a hole transporting material, a material capable of transporting holes from an anode or a hole injection layer to be transferred to a light emitting layer is a material having high mobility to holes. Specific examples include arylamine-based organics, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ), carbazole series compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazoles, benzthiazoles and Benzimidazole-based compounds, poly (p-phenylenevinylene) (PPV) -based polymers, spiro compounds, polyfluorenes, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes including Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

In addition, the organic light emitting compound according to the present invention may act on a similar principle to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

Synthesis Example  1: Synthesis of Compound 1

(One) Production Example  1: Synthesis of Intermediate 1-1

1-bromo-2-nitrobenzene (50 g, 0.247 mol, sigma aldrich), 2-bromophenylboronic acid (59.6 g, 0.297 mol, sigma aldrich), potassium carbonate (90.4 g, 0.94 mol, sigma aldrich), catalyst Pd (PPh ₃ ) ₄ (17.16 g, 0.015 mol, sigma aldrich) was added 400 mL of THF and 80 mL of water and stirred for 12 hours at 60 ℃. After completion of the reaction, the mixture was extracted and purified by column to obtain 66.7 g (yield 96%) of <Intermediate 1-1>.

(2) Production Example  2: synthesis of intermediate 1-2

Intermediate 1-1 (28 g, 0.1 mol), triphenylphosphine (79.2 g, 0.302 mol, sigma aldrich) and 1,2-dichlorobenzene 200 mL were added and reacted at 180 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column (N-HEXANE) to obtain 20 g (yield 80%) of <Intermediate 1-2>.

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

Intermediate 1-2 (10 g, 0.041 mol), 4-bromostyrene (8.9 g, 0.049 mol, TCI), potassium carbonate (14.04 g, 0.102 mol, sigma aldrich), Cu (5.16 g, 0.081 mol, sigma aldrich), Dibenzo-18-crown-6 (1.46 g, 0.004 mol, sigma Aldrich) and 150 mL of Dimethylformamide were added and stirred at 150 ° C. for 12 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 11 g (yield 77.7%) of <intermediate 1-3>.

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

Intermediate 1-3 (10 g, 0.029 mol), Bis (pinacolato) diboron (9.48 g, 0.037 mol, sigma aldrich), potassium acetate (5.64 g, 0.057 mol, sigma aldrich), PdCl ₂ (dppf) (0.63 g, 0.001 mol, sigma aldrich) and 400 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 8 g (yield 71.4%) of <Intermediate 1-4>.

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

Intermediate 1-4 (10 g, 0.025 mol), 1-boromo-4-iodobenzene (8.59 g, 0.030 mol, sigma aldrich), potassium carbonate (10.49 g, 0.076 mol, sigma aldrich), Pd (PPh ₃ ) ₄ ( 1.46 g, 0.0013 mol, sigma aldrich), THF 200 mL, and 60 mL of water were added and reacted at 60 ° C. for 12 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 8.3 g (yield 77.3%) of <Intermediate 1-5>.

(6) Production Example  6: synthesis of intermediate 1-6

Bromoaniline (10 g, 0.059 mol, sigma aldrich), 4-vinylphenylboronic acid (10.44 g, 0.071 mol, sigma aldrich), potassium carbonate (24.39 g, 0.176 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (3.4 g, 0.003 mol, sigma aldrich), THF 150 mL, and 30 mL of water were stirred and reacted at 60 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 8.5 g (74% yield) of <Intermediate 1-6>.

(7) Production Example  7: Synthesis of Intermediate 1-7

2-bromo-9,9-dimethyl-9H-fluorene (10 g, 0.037 mol, sigma aldrich), intermediate 1-6 (8.58 g, 0.044 mol), Sodium tert-butoxide (7.04 g, 0.073 mol, sigma aldrich) , 150 mL of Toluene was added to the catalyst Pd (dba) ₂ (0.74 g, 0.0018 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.74 g, 0.0037 mol, sigma aldrich) and stirred at 100 ° C. for 6 hours. I was. After completion of the reaction, the mixture was extracted and purified by column to obtain 11 g (yield 77.5%) of <Intermediate 1-7>.

(8) Production Example  8: Synthesis of Compound 1

Intermediate 1-5 (10 g, 0.024 mol), intermediate 1-7 (10.96 g, 0.028 mol), Sodium tert-butoxide (4.53 g, 0.047 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.68 g, 0.0012 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.48 g, 0.0024 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 6 hours. After completion of the reaction, extraction and column purification gave 13 g (yield 75.5%) of compound 1.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (8.12 / d, 8.10 / d, 7.90 / d, 7.87 / d, 7.63 / d, 7.62 / d, 7.55 / d, 7.50 / m, 7.39 / m, 7.29 / m, 7.28 / m, 6.75 / s, 6.58 / d) 2H (7.59 / d, 7.57 / d, 6.63 / m, 5.61 / d, 5.18 / d, 7.44 / d) 3H (7.38 / m) 4H (7.54 / d, 6.69 / d) 6H (1.72 / s)

LC / MS: m / z = 730 [(M + 1) ⁺ ]

Synthesis Example  2: Synthesis of Compound 26

Production Example  1: Synthesis of Intermediate 26-1

Bis (4-bromophenyl) amine (10 g, 0.031 mol, sigma aldrich), 4-vinylphenylboronic acid (9.95 g, 0.067 mol, sigma aldrich), potassium carbonate (16.91 g, 0.122 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.77 g, 0.0015 mol, sigma aldrich), 200 mL of THF, and 50 mL of water were added and stirred at 60 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 8.7 g (yield 76.2%) of <Intermediate 26-1>.

(2) Production Example  2: Synthesis of Compound 26

Intermediate 1-5 (10 g, 0.024 mol), intermediate 26-1 (10.56 g, 0.028 mol), Sodium tert-butoxide (4.53 g, 0.047 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.68 g, 0.0012 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.48 g, 0.0024 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 12 hours. After completion of the reaction, extraction and column purification gave 12.6 g (yield 74.6%) of compound 26.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (8.12 / d, 8.10 / d, 7.90 / d, 7.63 / d, 7.50 / m, 7.39 / m, 7.29 / m) 2H (7.57 / d, 7.38 / d ) 3H (6.63 / m, 5.61 / m, 5.18 / m) 4H (7.59 / d, 7.44 / d) 6H (7.54 / d, 6.69 / d)

LC / MS: m / z = 716 [(M + 1) ⁺ ]

Synthesis Example  3: Synthesis of Compound 64

(One) Production Example  1: Synthesis of Intermediate 64-1

2-iodophenol (10 g, 0.046 mol, sigma aldrich), 2-fluoro-6-iodophenylboronic acid (14.50 g, 0.055 mol, sigma aldrich), potassium carbonate (18.85 g, 0.136 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (2.63 g, 0.0023 mol, sigma aldrich), Toluene 150 mL, Ethanol 40 mL, H ₂ O 20 mL were added and reacted under reflux for 5 hours. After the completion of the reaction, extraction and column purification gave 11.4 g (yield 79.85%) of <Intermediate 64-1>.

(2) Production Example  2: Synthesis of Intermediate 64-2

Intermediate 64-2 (10 g, 0.032 mol), potassium carbonate (9.68 g, 0.070 mol, sigma aldrich) and N- Methyl-2-pyrrolidone 300 mL were added and reacted under reflux at 180 ° C. for 3 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 7.5 g (yield 80%) of <Intermediate 64-2>.

(3) Production Example  3: Synthesis of Intermediate 64-3

Intermediate 64-2 (10 g, 0.034 mol) and 200 mL of dichloromethane were added and cooled using an ice-bath. After slowly dropping bromine (6.52 g, 0.041 mol, sigma aldrich), the mixture was stirred for 1 hour and the ice-bath was removed. And reacted by stirring at room temperature for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 10 g (yield 78.8%) of <Intermediate 64-3>.

(4) Production Example  4: Synthesis of Intermediate 64-4

Intermediate 64-3 (10 g, 0.031 mol), 4-chlorophenylboronic acid (5.24 g, 0.034 mol, sigma aldrich), potassium acetate (12.64 g, 0.092 mol, sigma aldrich), PdCl ₂ (dppf) (1.76 g, 0.0015 mol, sigma aldrich), 200 mL of 1,4-Dioxane and stirred at 95 ℃ for 12 hours to react. After completion of the reaction, the mixture was extracted and purified by column to give 8.2 g (yield 75.2%) of <intermediate 64-4>.

(5) Production Example  5: synthesis of intermediate 64-5

Intermediate 644 (10 g, 0.028 mol), 4-vinylphenylboronic acid (4.97 g, 0.034 mol, sigma aldrich), potassium carbonate (11.59 g, 0.084 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.62 g, 0.0014 mol, sigma aldrich), 200 mL of THF, and 50 mL of water were added and reacted at 60 ° C. for 12 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 8 g (yield 75.1%) of <Intermediate 64-5>.

(6) Production Example  6: synthesis of intermediate 64-6

3-bromodibenzofuran (10 g, 0.041 mol, Mascot.), Intermediate 1-6 (9.48 g, 0.049 mol), Sodium tert-butoxide (7.78 g, 0.081 mol, sigma aldrich), Catalyst Pd (dba) ₂ (1.16 g , 0.002 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.82 g, 0.004 mol, sigma aldrich) were added 150 mL of toluene and stirred at 100 ° C. for 6 hours. After completion of the reaction, extraction and column purification gave 11 g (yield 75.2%) of <Intermediate 64-6>.

(7) Production Example  7: Synthesis of Compound 64

Intermediate 64-5 (10 g, 0.026 mol), Intermediate 64-6 (11.39 g, 0.032 mol), Sodium tert-butoxide (5.05 g, 0.053 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.75 g, 0.0013 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.53 g, 0.0026 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 12 hours. After completion of the reaction, extraction and column purification gave 13.7 g (yield 73.9%) of compound 64.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (7.87 / d, 7.68 / d, 7.64 / d, 7.43 / s, 6.33 / d) 2H (7.89 / d, 7.66 / d, 6.63 / m, 5.61 / m , 5.18 / m, 7.38 / m, 7.32 / m) 4H (7.59 / d, 7.54 / d, 7.44 / d, 6.69 / d)

LC / MS: m / z = 705 [(M + l) ⁺ ]

Synthesis Example  4: Synthesis of Compound 79

(One) Production Example  1: Synthesis of Intermediate 79-1

Intermediate 1-2 (10 g, 0.041 mol), 1,4-diiodobenzene (16.1 g, 0.049 mol, sigma aldrich), potassium carbonate (14.04 g, 0.102 mol, sigma aldrich), Cu (5.16 g, 0.081 mol, sigma aldrich), dibenzo-18-crown-6 (1.46 g, 0.004 mol, sigma aldrich) and 150 mL of dimethylformamide were added and stirred at 150 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 13 g (yield 71.4%) of <intermediate 79-1>.

(2) Production Example  2: Synthesis of Intermediate 79-2

Intermediate 79-1 (10 g, 0.022 mol), cyclobutabenzen-4-ylboronic acid (3.58 g, 0.025 mol, Mascot.), Potassium carbonate (9.25 g, 0.067 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.29 g, 0.0011 mol, sigma aldrich), 200 mL of THF, and 50 mL of water were added and reacted at 60 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 6.8 g (yield 72.1%) of <intermediate 79-2>.

(3) Production Example  3: Synthesis of Intermediate 79-3

Intermediate 79-2 (10 g, 0.024 mol), bis (pinacolato) diboron (7.82 g, 0.031 mol, sigma aldrich), potassium acetate (4.65 g, 0.047 mol, sigma aldrich), PdCl ₂ (dppf) (0.52 g, 0.0007 mol, sigma aldrich) and 400 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 7.7 g (69.2%) of <Intermediate 79-3>.

(4) Production Example  4: Synthesis of Intermediate 79-4

Intermediate 79-3 (10 g, 0.021 mol), 1-boromo-3-iodobenzene (7.23 g, 0.026 mol, sigma aldrich), potassium carbonate (8.83 g, 0.064 mol, sigma aldrich), Pd (PPh ₃ ) ₄ ( 1.23 g, 0.0011 mol, sigma aldrich), 200 mL of THF, and 60 mL of water were added and reacted at 60 ° C. for 12 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 8 g (yield 75.3%) of <Intermediate 79-4>.

(5) Production Example  5: Synthesis of Intermediate 79-5

4-Bromoaniline (10 g, 0.058 mol, sigma aldrich), cyclobutabenzen-4-ylboronic acid (10.18 g, 0.070 mol, Mascot.), Potassium carbonate (24.10 g, 0.174 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (3.36 g, 0.0029 mol, sigma aldrich), 200 mL of THF, and 50 mL of water were added and reacted at 60 ° C. for 12 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 8.2 g (yield 73%) of <intermediate 79-5>.

(6) Production Example  6: synthesis of intermediate 79-6

4-bromodibenzofuran (10 g, 0.041 mol, sigma aldrich), intermediate 79-5 (8.60 g, 0.045 mol), Sodium tert-butoxide (7.78 g, 0.081 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.16 g , 0.002 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.82 g, 0.004 mol, sigma aldrich) were added 150 mL of toluene and stirred at 100 ° C. for 6 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 11 g (yield 75.6%) of <intermediate 79-6>.

(7) Production Example  7: Synthesis of Compound 79

Intermediate 79-4 (10 g, 0.020 mol), intermediate 79-6 (7.93 g, 0.022 mol), Sodium tert-butoxide (3.86 g, 0.040 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.58 g, 0.001 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.41 g, 0.002 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 12 hours. After completion of the reaction, extraction and column purification gave 11.6 g (yield 74.4%) of compound 79.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (8.55 / d, 7.94 / d, 7.89 / d, 7.66 / d, 7.59 / d, 7.44 / m, 7.43 / m, 7.38 / m, 7.33 / m, 7.32 / m, 7.07 / m, 6.89 / s, 6.88 / d, 6.59 / d, 6.39 / d) 2H (7.90 / s, 7.68 / d, 7.54 / d, 7.47 / d, 7.39 / d, 7.25 / m, 6.69 / d) 3H (7.79 / d) 4H (6.56 / d)

LC / MS: m / z = 776 [(M + 1) ⁺ ]

Device Example

In an embodiment according to the present invention, the ITO transparent electrode is patterned on a glass substrate of 25 mm × 25 mm × 0.7 mm, using an ITO glass substrate with an ITO transparent electrode, so that the light emitting area is 2 mm × 2 mm in size. And then washed. The substrate was mounted in a vacuum chamber, and the base pressure was 1 × 10 ⁻⁶ torr. Then, the organic material and the metal were deposited on the ITO with the following structure.

Device Examples 1-9

Using the compound implemented according to the present invention as a compound of the hole transport layer, a blue light emitting organic electroluminescent device having a device structure as described below was manufactured, and light emission characteristics including light emission efficiency were measured.

ITO / PEDOT: PSS (50 nm) / hole transport layer (30 nm) / light emitting layer (30 nm) / electron transport layer (Alq 40 nm) / LiF (0.5 nm) / Al (150 nm)

After spin-coating PEDOT: PSS to 50 nm thickness on an ITO transparent electrode and drying for 10 minutes on a hot plate at 150 ° C. to remove the solvent, the compound according to the present invention, a hole transport material, is dissolved in toluene and spin to 30 nm thickness. -coating Then, dried for 10 minutes on a hot plate of 100 ℃, crosslinked by heating for 50 minutes at 220 ℃. As a light emitting layer host on the hole transport layer, dopant BH1 was doped with BD1 96: 4, spin-coated a solution dissolved in toluene to a thickness of 30 nm, dried on a hot plate at 100 ° C for 10 minutes, and then mounted in a vacuum chamber. Set the pressure to 1 × 10 ^-6 torr. Thereafter, tris (8-quinolinol) aluminum (Alq ₃ ) was deposited to a thickness of 40 nm as an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.5 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic light emitting diode.

Device comparison example 1

An organic light emitting display device according to Comparative Example 1 was manufactured in the same manner as in Example 1 except that <Compound Compound 1> was used instead of the compound of the present invention in the hole transport layer.

Experimental Example 1 Luminescence Characteristics of Device Examples 1 to 9

In the organic light emitting diode manufactured according to the above embodiment, voltage, current, and luminous efficiency were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA / cm 2. The voltage to be defined as "drive voltage" was compared. The results are shown in the following [Table 1].

Example Hole transport layer V cd / A CIEx CIEy One Formula 1 4.26 6.66 0.143 0.153 2 Formula 11 4.52 5.69 0.145 0.154 3 Formula 23 4.38 5.95 0.144 0.155 4 Formula 26 4.24 6.83 0.143 0.152 5 Formula 34 4.45 5.86 0.144 0.154 6 Formula 45 4.36 6.42 0.144 0.155 7 Formula 64 4.39 6.38 0.145 0.154 8 Formula 75 4.60 5.67 0.146 0.156 9 Formula 79 4.44 6.29 0.145 0.154 Comparative Example 1 <Comparative Compound 1> 6.17 4.40 0.145 0.156

Looking at the results shown in [Table 1], it can be seen that, first, in the case of applying the compound according to the present invention to the hole transport layer, the light emission characteristics such as driving voltage and luminous efficiency are remarkably superior to those of the conventional device (Comparative Example 1). .

[PEDOT: PSS]   [BH1]    [BD1]  [Comparative Compound 1]

Claims (8)

An organic light emitting compound represented by any one selected from the following [Formula I] to [Formula IV]:
[Formula I]

[Formula II]

[Formula III]

[Formula IV]

In [Formula I] to [Formula IV],
L ₁ , L ₂ and L ₃ are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted fluorene Selected from the ylene groups, l, n and m are each an integer of 1 to 3 (when a plurality of L ₁ , L ₂ and L ₃ are the same or different from each other when l, n and m are each 2 or more),
Ar ₁ , Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted hetero atom having 2 to 30 carbon atoms. Selected from aryl groups,
Ar ₁ , Ar ₂ and Ar ₃ may be bonded to each other or connected to an adjacent substituent to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring are N , May be substituted with any one or more heteroatoms selected from S and O,
o, p and q are each an integer of 1 to 3, when o, p and q is 2 or more, a plurality of Ar ₁ to Ar ₃ may be the same or different from each other,
A ₁ to A ₅ are each independently hydrogen, deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, carbonyl group, ether group, silane group, siloxane group, substituted or unsubstituted C 1-20 Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms , Substituted or unsubstituted fluorenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms , Substituted or unsubstituted C 1 -C 20 alkoxy group, substituted or unsubstituted C 1 -C 20 alkylsilyl group, substituted or unsubstituted C 6 -C 30 arylsilyl group, substituted or Unsubstituted C7-30 arylalkyl group, substituted or unsubstituted C2-30 alkenyloxyl group, substituted or unsubstituted C8-30 alkenylaryl group, substituted or unsubstituted C7-30 An arylalkoxy group, a substituted or unsubstituted arylalkenyl group having 8 to 30 carbon atoms and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms,
The term 'substituted', L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ , Ar ₃ And A ₁ to A ₅ are each further substituted with at least one substituent, and the at least one substituent is deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, carbonyl group, ether group, silane group, Siloxane groups, alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 3 to 20 carbon atoms, alkenyl groups of 2 to 20 carbon atoms, alkynyl groups of 2 to 20 carbon atoms, halogenated alkyl groups of 1 to 20 carbon atoms, fluorenyl groups, and 6 carbon atoms An aryl group having 30 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, Arylalkyl group having 7 to 30 carbon atoms, alkenyloxyl group having 2 to 30 carbon atoms, alkenylaryl group having 8 to 30 carbon atoms, arylalkoxy group having 7 to 30 carbon atoms, arylalkenyl group having 8 to 30 carbon atoms, and carbon atoms It is selected from alkoxycarbonyl group of 2-20. The method of claim 1,
At least one of A ₁ to A ₃ in [Formula I]; At least one of A ₁ and A ₄ in [Formula II]; At least one of A ₁ to A ₃ and A ₅ in [Formula III]; At least one of A ₁ , A ₄ and A ₅ in [Formula IV];
Vinyl, acryloyl, methacryloyl, cyclic ethers, siloxanes, styrenes, trifluorovinyl ethers, benzo [Chemical Formulas I] to [IV] include crosslinking properties including at least one crosslinking group selected from benzocyclo-butenes, cinnamates, chalcones, and oxetanes. An organic light emitting compound having a. The method of claim 1,
At least one of A ₁ to A ₃ in [Formula I]; At least one of A ₁ and A ₄ in [Formula II]; At least one of A ₁ to A ₃ and A ₅ in [Formula III]; At least one of A ₁ , A ₄ and A ₅ in the formula [IV];
An organic light emitting compound comprising a substituent structure of any one structure selected from the following [Formula 1] and two or more selected and connected to each other:
[Formula 1]

The method of claim 1,
In the following structures respectively introduced in [Formula I] and [Formula III], at least one of Ar ₁ and Ar ₂ is an organic light emitting compound, characterized in that any one selected from the following [formula 2]:

[Formula 2]

The method of claim 1,
[Formula I] to [Formula IV] is an organic light emitting compound, characterized in that selected from the following [Compound 1] to [Compound 82]:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the organic light emitting compound of [Formula I] to [Formula IV] according to claim 1. The method of claim 6,
The organic material layer includes one or more layers selected from a hole injection layer, a hole transport layer, a layer simultaneously performing hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer simultaneously performing electron transport and electron injection functions, and a light emitting layer.
Organic light emitting device, characterized in that at least one of the layers comprises an organic light emitting compound represented by the above [Formula I] to [Formula IV]. The method of claim 7, wherein
The organic layer is formed by a solution process, the solution process is an organic light emitting device, characterized in that any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process.

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