KR20180066855A - Novel amine-based compound and organic light emitting device comprising the same - Google Patents

Abstract

According to the present invention, provided are a novel amine-based compound, and an organic light emitting device including the same. The compound of the present invention is represented by chemical formula 1. In chemical formula 1, L_1 and L_2 are independently a single bond, L_3 is a single bond, or a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, and Ar_1 is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthrenyl, dimethyl fluorenyl, methyl phenyl fluorenyl, diphenyl fluorenyl, dibenzofuranyl, or dibenzothiophenyl. Therefore, the compound of the present invention is able to be used as a material for an organic layer of an organic light emitting device, and improve efficiency and low driving voltage and/or lifespan characteristics of the organic light emitting device.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel amine compound, and an organic light emitting device comprising the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel amine compound compound and an organic light emitting device comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. The organic material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention provides novel amine-based compounds.

The present invention also provides an organic light emitting device comprising a novel amine compound.

The present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently a single bond; A halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 40 carbon atoms, and an arylene group having 6 to 40 carbon atoms substituted or unsubstituted with a heteroalkyl group having 1 to 40 carbon atoms and containing at least one of O, N, ; O, N, Si and / or a substituted or unsubstituted C1 to C40 heteroalkyl group containing at least one of a halogen, a nitro group, a cyano group, an alkyl group having 1 to 40 carbon atoms, and O, N, S < / RTI > having from 2 to 60 carbon atoms,

L ₃ is a single bond; Or a substituted or unsubstituted arylene group having 6 to 40 carbon atoms,

Ar ₁ is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, dimethylfluorenyl, methylphenylfluorenyl, diphenylfluorenyl, dibenzofuranyl, or dibenzothiophenyl to be.

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1, to provide.

The compound represented by the general formula (1) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device. The compound represented by the formula (1) can be used as a hole injecting, hole transporting, hole injecting and transporting, luminescence, electron transporting, or electron injecting material, and in particular, as a hole transporting or electron blocking material.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The present invention provides a compound represented by the above formula (1).

In the present specification, a single bond means a case where there is no separate atom at a portion represented by L ₁ , L ₂ , or L ₃ . For example, the L ₁ and L ₂ in formula (1) can be connected directly to the two triphenylene is a single bond N.

Halogen in this specification may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group having 1 to 40 carbon atoms may be a straight chain, branched chain or cyclic alkyl group. Specifically, the alkyl group having 1 to 40 carbon atoms is preferably a straight chain alkyl group having 1 to 40 carbon atoms; A straight chain alkyl group having 1 to 20 carbon atoms; A straight chain alkyl group having 1 to 10 carbon atoms; Branched or cyclic alkyl group having 3 to 40 carbon atoms; Branched or cyclic alkyl group of 3 to 20 carbon atoms; Or a branched or cyclic alkyl group having 3 to 10 carbon atoms. More specifically, the alkyl group having 1 to 40 carbon atoms is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a neopentyl group, a cyclohexyl group, or the like. However, the present invention is not limited thereto.

In the present specification, the heteroalkyl group having 1 to 40 carbon atoms may be one in which at least one carbon of the alkyl group is independently substituted with O, N, Si or S; Examples of the straight chain alkyl group include a n-propoxy group, a n-propoxy group, a n-propoxy group, and a heteroalkyl group substituted by Si, -Propylsilyl group, and the heteroalkyl group substituted by S is an n-propylthio group. Examples of the branched alkyl group include a heteroalkyl group in which the carbon atom of the neopentyl group is substituted by O is t-butoxy group, a heteroalkyl group substituted by N is t-butylamino group, and a heteroalkyl group substituted by Si is t Butylsilyl group, and the heteroalkyl group substituted by S is a t-butylthio group. Examples of the cyclic alkyl group include a 2-tetrahydropyranyl group in which the carbon atom of the cyclohexyl group is substituted with O is a 2-tetrahydropyranyl group, a heteroalkyl group substituted by N is a 2-piperidinyl group, The heteroalkyl group substituted by Si is a 1-sila-cyclohexyl group, and the heteroalkyl group substituted by S is a 2-tetrahydrothiopyranyl group. Specifically, the heteroalkyl group having 1 to 40 carbon atoms is preferably a straight chain, branched chain or cyclic hydroxyalkyl group having 1 to 40 carbon atoms; A linear, branched or cyclic alkoxy group having 1 to 40 carbon atoms; A linear, branched or cyclic alkoxyalkyl group having 2 to 40 carbon atoms; A straight chain, branched chain or cyclic aminoalkyl group having 1 to 40 carbon atoms; A straight chain, branched chain or cyclic alkylamino group having 1 to 40 carbon atoms; A straight chain, branched chain or cyclic alkylaminoalkyl group having 1 to 40 carbon atoms; A linear, branched or cyclic silylalkyl (oxy) group having 1 to 40 carbon atoms; A straight, branched or cyclic alkyl (oxy) silyl group having 1 to 40 carbon atoms; A straight, branched or cyclic alkyl (oxy) silylalkyl (oxy) group having 1 to 40 carbon atoms; A linear, branched or cyclic mercaptoalkyl group having 1 to 40 carbon atoms; A straight, branched or cyclic alkylthio group having 1 to 40 carbon atoms; Or a straight chain, branched chain or cyclic alkylthioalkyl group having 2 to 40 carbon atoms. More specifically, the heteroalkyl group having 1 to 40 carbon atoms is preferably a hydroxymethyl group, a methoxy group, an ethoxy group, an n-propoxy group, an iso- propoxy group, a t-butoxy group, a cycloheptoxy group, a methoxymethyl group, A 2-tetrahydropyranyl group, an aminomethyl group, a methylamino group, a n-propylamino group, a t-butylamino group, a methylaminopropyl group, a 2-piperidinyl group, a n- Butylsilyl group, a 1-sila-cyclohexyl group, a n-propylthio group, a t-butylthio group or a 2-tetrathiethylthio group. And 2-tetrahydrothiopyranyl group. However, the present invention is not limited thereto.

In the present specification, the arylene group having 6 to 60 carbon atoms may be a monocyclic arylene group or a polycyclic arylene group. Specifically, the arylene group having 6 to 60 carbon atoms is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; Or a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms. More specifically, the arylene group having 6 to 60 carbon atoms may be a divalent residue derived from areene selected from the group consisting of benzene, biphenyl and terphenyl as a monocyclic arylene group, and the like, and naphthalene, anthracene, phenanthrene , Divalent residue derived from areene selected from the group consisting of triphenylene, pyrene, perylene, klycene and fluorene, and the like. However, the present invention is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, fluorene may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorene is substituted,

And the like. However, the present invention is not limited thereto.

In the present specification, the heteroarylene group having 2 to 60 carbon atoms may be one in which at least one carbon of the arylene group is independently substituted with O, N, Si, or S. For example, the heteroarylene group in which the 9-carbon of the fluorene-derived divalent moiety is substituted with O is a divalent residue derived from dibenzofuran, the heteroarylene group substituted with N is a divalent residue derived from carbazole, and Si Is a divalent residue derived from 9-sila-fluorene, and the heteroarylene group substituted with S is a divalent residue derived from dibenzothiophene. Specifically, the heteroarylene group having 2 to 60 carbon atoms is a heteroarylene group having 2 to 30 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms. More specifically, the heteroarylene group having 2 to 60 carbon atoms may be substituted with one or more groups selected from thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridine, bipyridine, pyrimidine, Wherein the compound is selected from the group consisting of acridine, pyridazine, pyrazine, quinoline, quinazoline, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, pyrazinopyrazine, isoquinoline, indole, carbazole, benzoxazole, Benzothiazole, phenothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiophene, benzothiophene, benzofuran, phenanthroline, thiazole, isoxazole, oxadiazole, And a divalent residue derived from heteroarene composed of dibenzofuran, but the present invention is not limited thereto.

The compound represented by Formula 1 may be represented by Formula 2 below.

(2)

In Formula 2, L ₁ , L ₂ , L ₃ and Ar _{1 have} the same definitions as in Formula 1.

In the general formulas (1) and (2), L ₁ and L ₂ each independently represent a single bond or an arylene group having 6 to 40 carbon atoms. Specifically, L ₁ and L ₂ are each independently a single bond or an arylene group having 6 to 18 carbon atoms. More specifically, L ₁ and L ₂ may each independently be a single bond or a phenylene group.

L ₃ represents a single bond, phenylene, phenanthrenediyl, dimethylfluorenediyl, methylphenylfluorenediyl, diphenylfluorenediyl, phenylene-phenanthrenediyl, phenylene-dimethylfluorenediyl, phenylene- Fluorenediyl, or phenylene-diphenylfluorenediyl.

The compounds represented by the above formulas (1) and (2) may be selected from the group consisting of the following compounds.

The compound represented by the formula (1) can be prepared by the following reaction scheme (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1, the definitions of L ₁ , L ₂ , L ₃ and Ar ₁ are as defined above, and X is halogen, more preferably bromo, or chloro.

Each of the above reactions is preferably an amine substitution reaction in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be modified as known in the art. The above production method can be more specific in the production example to be described later.

Also, the present invention provides an organic light emitting device including the compound represented by Formula 1. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole transporting layer or an electron blocking layer, and the hole transporting layer or the electron blocking layer may include a compound represented by the above formula (1).

The organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the compound represented by Formula 1 may be included in the hole transport layer.

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula (1). In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable.

The compound represented by the above formula (1) is excellent in this ability and can be used as a hole transport material. However, the hole transport layer included in the organic light emitting device of the present invention may further include various hole transport materials known in the art to which the present invention belongs, in addition to the compound represented by the above formula (1). Specific examples of such conventional hole transporting materials include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

[ Example ]

Example  1: Preparation of compound 1

(19 g, 64.4 mmol) and NaOt-Bu (7.4 g, 77.28 mmol) were added to toluene (160 ml) and stirred at 110 占 폚 . After the temperature was elevated, reflux was begun and bis (tri-tert-butylphosphine) palladium (0.32 g, 0.64 mmol) was slowly added dropwise. After the reaction was carried out for 5 hours, the temperature was lowered to room temperature, and the mixture was concentrated under reduced pressure and then subjected to column purification to obtain Compound 1 (13.1 g, yield 75%).

MS: [M + H] < ⁺ > = 546

Example  2: Preparation of compound 2

Compound 2 was prepared (8.02 g, yield 73%) in the same manner as in the preparation of Compound 1, except that [1,1'-biphenyl] -2-amine (3 g, 17.7 mmol) ).

MS: [M + H] < ⁺ > = 622

Example  3: Preparation of compound 3

Compound 3-1 was prepared (1.74 g, yield 64%) in the same manner as in the preparation of Compound 1, except that triphenylene-2-amine (3 g, 5.79 mmol) was used instead of aniline.

A solution of Compound 1 (1.74 g, 3.71 mmol) and Intermediate 3-1 (1.74 g, 3.71 mmol) was used, except that 5'-bromo-1,1 ': 3' Compound 3 (1.89 g, yield 73%) was prepared in the same manner as the preparation method.

MS: [M + H] < ⁺ > = 698

Example  4: Preparation of compound 4

(3 g, 9.29 mmol), triphenylene-2-ylboronic acid (2.53 g, 9.29 mmol), and tetrakis (triphenylphosphine) (Triphenylphosphine) palladium (2 mol%) were dissolved in tetrahydrofuran (20 ml) and potassium carbonate (18.58 mmol) was dissolved in water (10 ml) and mixed. After stirring at 80 ° C for 6 hours, the reaction was terminated and the reaction mixture was cooled to room temperature to separate water and an organic layer. After recovering only the organic layer, anhydrous magnesium sulfate was added and stirred. The mixture was filtered through a silica pad, concentrated under reduced pressure, and purified by column to obtain Intermediate 4-1 (3.54 g, yield 81%).

Compound 4 (3.19 g, yield 61%) was prepared in the same manner as in the preparation of Compound 1, except that Intermediate 4-1 (3.54 g, 7.51 mmol) was used.

MS: [M + H] < ⁺ > = 698

Example  5: Preparation of compound 5

The same procedure for the intermediate 4-1 was repeated except that 2-bromotriphenylene (3 g, 9.80 mmol) and (4-chlorophenyl) boronic acid (1.53 g, 9.80 mmol) 5-1 (2.55 g, yield 77%).

 Except that Intermediate 5-1 (2.55 g, 7.39 mmol) and [1,1 ': 4', 1 "-terphenyl] -2- amine (0.90 g, 3.69 mmol) Compound 5 (1.85 g, yield 59%) was prepared in the same manner as in the method of Example 1,

MS: [M + H] < ⁺ > = 850

Example  6: Preparation of Compound 6

Except that 9,9-dimethyl-9H-fluorene-2-amine (3 g, 14.3 mmol) and 2-bromotriphenylene (2.19 g, 7.15 mmol) Compound 6 (3.07 g, yield 65%) was prepared in the same manner.

MS: [M + H] < ⁺ > = 662

Example  7: Preparation of Compound 7

9,9-diphenyl-9H-fluorene-2-amine (3 g, 9.00 mmol) was dissolved completely in dimethylformamide (20 ml) and cooled to 0 ° C using an ice bath. N-Bromosuccinimide (1.67 g, 9.45 mmol) was slowly added dropwise thereto and stirred. The reaction solution was poured into water (100 ml) and stirred for 1 hour. Tetrahydrofuran (100 ml) was added and stirred. Only the organic solution was recovered and concentrated under reduced pressure to prepare Intermediate 7-1 (2.40 g, yield 65%).

Intermediate 7-2 (1.74 g, yield: 82%) was obtained in the same manner as in the preparation of Intermediate 4-1, except that Intermediate 7-1 (2.4 g, 5.84 mmol) and phenylboronic acid (0.71 g, 73%).

Compound (7) (2.01 g, yield: 82%) was obtained in the same manner as the compound 1, except that Intermediate 7-2 (1.74 g, 4.25 mmol) and 2-bromotriphenylene 55%).

MS: [M + H] < ⁺ > = 862

Example  8: Preparation of compound 8

Compound 8 (1.00 g) was obtained in the same manner as the compound 1, except that Intermediate 3-1 (3 g, 6.39 mmol) and 4-bromodibenzo [b, 2.92 g, yield 72%).

MS: [M + H] < ⁺ > = 636

Example  9: Preparation of compound 9

(2.88 g, yield 70%) was obtained in the same manner as in the preparation of Compound 1, except that Intermediate 3-1 (3 g, 6.39 mmol) and 9-bromophenanthrene (1.63 g, %).

MS: [M + H] < ⁺ > = 646

Example  10: Preparation of compound 10

Except that the intermediate 4- (4-bromophenyl) triphenylene-2-amine (3 g, 7.55 mmol) and triphenylene-2-ylboronic acid (2.05 g, Intermediate 10-1 (3.33 g, yield 81%) was prepared in the same manner as in the preparation of Intermediate 1.

The same procedure as that for preparing Compound 1 was repeated except for using Intermediate 10-1 (3.33 g, 6.11 mmol) and 2-bromo-9,9-diphenyl-9H-fluorene (2.42 g, 6.11 mmol) To give Compound 10 (2.89 g, yield 55%).

MS: [M + H] < ⁺ > = 862

Example  11: Preparation of compound 11

Compound 11 (2.54 g, yield 69%) was prepared in the same manner as the compound 1, except that Intermediate 10-1 (3 g, 5.50 mmol) and 2-bromonaphthalene (1.13 g, 5.50 mmol) ).

MS: [M + H] < ⁺ > = 672

Example  12: Preparation of compound 12

Intermediate 12-1 (2.46 g, yield 60%) was obtained in the same manner as in the preparation of Intermediate 7-1, except that 9,9-dimethyl-9H- %).

Intermediate 12-2 (1.78 g, yield: 82%) was obtained in the same manner as in the preparation of Intermediate 7-2, except that Intermediate 12-1 (2.46 g, 8.57 mmol) and phenylboronic acid (1.04 g, 8.57 mmol) 73%).

Compound 12 (3.22 g, yield 58%) was obtained in the same manner as the compound 1, except that Intermediate 12-2 (1.78 g, 6.24 mmol) and Intermediate 5-1 (4.22 g, 12.48 mmol) .

MS: [M + H] < ⁺ > = 890

Example  13: Preparation of compound 13

(3.03 g, yield 58%) was obtained in the same manner as the compound 1, except that naphthalene-2-amine (1 g, 6.99 mmol) and Intermediate 5-1 (4.7 g, 13.9 mmol) ).

MS: [M + H] < ⁺ > = 748

Example  14: Preparation of compound 14

Preparation of intermediate 4-1 was carried out except that 2-bromo dibenzo [b, d] thiophene (5.03 g, 19.2 mmol) was used instead of 2-bromo dibenzoic acid (3 g, 19.2 mmol) , Intermediate 14-1 (3.72 g, yield 66%) was prepared.

(5.58 g, yield 61%) was obtained in the same manner as the compound 1, except that Intermediate 14-1 (3.72 g, 12.6 mmol) and Intermediate 3-1 (5.91 g, 12.6 mmol) .

MS: [M + H] < ⁺ > = 728

Example  15: Preparation of compound 15

Compound 15 (2.26 g, 5.50 mmol) was obtained in the same manner as in the aforementioned compound 1, except that Intermediate 10-1 (3 g, 5.50 mmol) and 1- (4-bromophenyl) g, yield 55%).

MS: [M + H] < ⁺ > = 748

Example  16: Preparation of compound 16

Except that 4-bromoaniline (1 g, 5.85 mmol) and 9-methyl-9-phenyl-9H-fluoren-2-yl) boronic acid (1.76 g, 5.85 mmol) Intermediate 16-1 (1.56 g, yield 77%) was prepared in the same manner as in the production method of 1.

Compound 16 (2.69 g, yield 63%) was obtained in the same manner as in the preparation of Compound 1, except that Intermediate 16-1 (1.56 g, 4.49 mmol) and Intermediate 5-1 (3.04 g, 8.98 mmol) .

MS: [M + H] < ⁺ > = 952

[ Experimental Example ]

Experimental Example  1-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water, which was secondly filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HAT compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. Compound 1 prepared above was vacuum deposited on the hole injection layer to a thickness of 1160 ANGSTROM to form a hole transport layer. The following EB1 compound was vacuum deposited on the hole transport layer to a thickness of 100 Å to form an electron blocking layer. The following BH compound and BD compound shown below were vacuum deposited on the electron blocking layer at a weight ratio of 25: 1 to a thickness of 300 ANGSTROM to form a light emitting layer. The following ET1 compound and the following LiQ compound were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to a thickness of 300 Å to form an electron injection and transport layer. Aluminum was sequentially deposited on the electron injecting and transporting layer to a thickness of 12 Å and lithium aluminum fluoride (LiF) to a thickness of 2,000 Å to form a cathode.

Was maintained at a vapor deposition rate of 0.4 to 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- 7} to 5 x 10 < ^-6 > torr to produce an organic light emitting device.

Experimental Example  1-2 to 1-16

An organic light emitting device was prepared in the same manner as in Experimental Example 1-1, except that the compound described in Table 1 was used instead of Compound 1.

Comparative Experimental Example  1-1 to 1-3

An organic light emitting device was prepared in the same manner as in Experimental Example 1-1, except that the compound described in Table 1 was used instead of Compound 1. In Table 1, C1, C2, and C3 are as follows.

The voltage, efficiency and color coordinates were measured by applying current to the organic light emitting device manufactured in the Experimental Examples and Comparative Experimental Examples. The results are shown in Table 1 below.

division compound
(Hole transport layer) Voltage (V)
(@ 10 mA / cm ² ) Efficiency (cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Experimental Example 1-1 Compound 1 4.55 5.75 (0.139, 0.122) Experimental Example 1-2 Compound 2 4.52 5.78 (0.138, 0.126) Experimental Example 1-3 Compound 3 4.30 5.96 (0.138, 0.127) Experimental Examples 1-4 Compound 4 4.31 5.94 (0.137, 0.125) Experimental Examples 1-5 Compound 5 4.59 5.73 (0.136, 0.125) Experimental Example 1-6 Compound 6 4.54 5.77 (0.136, 0.127) Experimental Example 1-7 Compound 7 4.50 5.78 (0.136, 0.125) Experimental Examples 1-8 Compound 8 4.44 5.71 (0.137, 0.125) Experimental Examples 1-9 Compound 9 4.43 5.78 (0.138, 0.125) Experimental Example 1-10 Compound 10 4.44 5.72 (0.136, 0.125) Experimental Example 1-11 Compound 11 4.43 5.77 (0.137, 0.125) Experimental Example 1-12 Compound 12 4.45 5.85 (0.136, 0.125) Experimental Example 1-13 Compound 13 4.42 5.88 (0.138, 0.126) Experimental Example 1-14 Compound 14 4.37 5.81 (0.137, 0.125) Experimental Example 1-15 Compound 15 4.38 5.82 (0.136, 0.127) Experimental Example 1-16 Compound 16 4.39 5.83 (0.135, 0.127) Comparative Experimental Example 1-1 C1 4.96 5.13 (0.136, 0.127) Comparative Experimental Example 1-2 C2 5.05 5.04 (0.136, 0.127) Comparative Experimental Example 1-3 C3 5.02 5.14 (0.136, 0.127)

As shown in Table 1, it was confirmed that the organic light emitting devices of Experimental Examples 1-1 to 1-16 exhibited lower voltage and higher efficiency than the organic light emitting devices of Comparative Examples 1-1 to 1-3.

Experimental Example  2-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HAT compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. Compound 1 prepared above was vacuum-deposited on the hole injection layer to a thickness of 400 Å to form a hole transport layer. On the hole transporting layer, the following RH compound and RD compound shown below were vacuum deposited at a weight ratio of 98: 2 to a thickness of 300 ANGSTROM to form a light emitting layer. The following E1 compound was vapor-deposited in a thickness of 300 Å on the light-emitting layer to form an electron transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above procedure, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of LiF was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec

Experimental Example  2-2 to 2-16

An organic light emitting device was prepared in the same manner as in Experimental Example 2-1, except that the compound described in Table 2 was used instead of Compound 1.

Comparative Experimental Example  2-1 to 2-3

An organic light emitting device was prepared in the same manner as in Experimental Example 2-1, except that the compound described in Table 2 was used instead of Compound 1. In Table 2, C1, C2, and C3 are as described in Comparative Experimental Examples 1-1 to 1-3.

The voltage, efficiency, and color coordinates were measured by applying current to the organic light emitting device manufactured in the Experimental Examples and Comparative Experimental Examples, and the results are shown in Table 2 below.

division compound
(Hole transport layer) Voltage (V)
(@ 10 mA / cm ² ) Efficiency (cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Experimental Example 2-1 Compound 1 4.71 23.75 (0.661, 0.332) EXPERIMENTAL EXAMPLE 2-2 Compound 2 4.74 23.18 (0.661, 0.331) Experimental Example 2-3 Compound 3 4.71 24.69 (0.664, 0.332) Experimental Example 2-4 Compound 4 4.73 23.49 (0.662, 0.332) Experimental Example 2-5 Compound 5 4.79 22.37 (0.661, 0.333) Experimental Examples 2-6 Compound 6 4.75 23.47 (0.661, 0.335) Experimental Example 2-7 Compound 7 4.77 23.87 (0.664, 0.332) Experimental Examples 2-8 Compound 8 4.71 22.74 (0.666, 0.331) Experimental Examples 2-9 Compound 9 4.87 23.15 (0.662, 0.334) Experimental Example 2-10 Compound 10 4.82 22.44 (0.661, 0.331) Experimental Example 2-11 Compound 11 4.81 22.71 (0.661, 0.333) Experimental Examples 2-12 Compound 12 4.88 23.86 (0.661, 0.330) Experimental Example 2-13 Compound 13 4.89 22.17 (0.664, 0.334) Experimental Example 2-14 Compound 14 4.77 21.05 (0.665, 0.332) Experimental Example 2-15 Compound 15 4.73 24.61 (0.664, 0.332) Experimental Example 2-16 Compound 16 4.77 23.18 (0.661, 0.331) Comparative Experimental Example 2-1 C1 5.24 20.41 (0.661, 0.338) Comparative Experimental Example 2-2 C2 5.30 20.10 (0.659, 0.331) Comparative Experimental Example 2-3 C3 5.28 19.89 (0.668, 0.332)

As shown in Table 2, it was found that the organic light emitting devices of Experimental Examples 2-1 to 2-16 exhibited lower voltage and higher efficiency than the organic light emitting devices of Comparative Examples 2-1 to 2-3.

Experimental Example  3-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HAT compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. The HT1 compound shown below was vacuum deposited on the hole injection layer to a thickness of 1160 Å to form a hole transport layer. Compound 1 prepared above was vacuum deposited on the hole transport layer to a thickness of 100 Å to form an electron blocking layer. The following BH compound and BD compound shown below were vacuum deposited on the electron blocking layer at a weight ratio of 25: 1 to a thickness of 300 ANGSTROM to form a light emitting layer. The following ET1 compound and the following LiQ compound were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to a thickness of 300 Å to form an electron injection and transport layer. Aluminum was sequentially deposited on the electron injecting and transporting layer to a thickness of 12 Å to a thickness of 2,000 Å to form a negative electrode.

Was maintained at a vapor deposition rate of 0.4 to 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- 7} to 5 x 10 < ^-6 > torr to produce an organic light emitting device.

Experimental Example  3-2 to 3-16

An organic light emitting device was prepared in the same manner as in Experimental Example 3-1 except that the compound described in Table 3 was used in place of Compound 1.

Comparative Experimental Example  3-1 to 3-3

An organic light emitting device was prepared in the same manner as in Experimental Example 2-1, except that the compound described in Table 3 was used instead of Compound 1. In Table 3, C1, C2, and C3 are as described in Comparative Experimental Examples 1-1 to 1-3.

The voltage, efficiency and color coordinates were measured by applying current to the organic light emitting device manufactured in the Experimental Example and Comparative Experimental Example, and the results are shown in Table 3 below.

division compound
(Electron blocking layer) Voltage (V)
(@ 10 mA / cm ² ) Efficiency (cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Experimental Example 3-1 Compound 1 4.14 5.85 (0.139, 0.122) Experimental Example 3-2 Compound 2 4.12 5.88 (0.138, 0.126) Experimental Example 3-3 Compound 3 4.10 5.86 (0.138, 0.127) Experimental Example 3-4 Compound 4 4.11 5.84 (0.137, 0.125) Experimental Example 3-5 Compound 5 4.19 5.83 (0.136, 0.125) Experimental Example 3-6 Compound 6 4.14 5.87 (0.136, 0.127) Experimental Example 3-7 Compound 7 4.10 5.88 (0.136, 0.125) Experimental Examples 3-8 Compound 8 4.14 5.81 (0.137, 0.125) Experimental Examples 3-9 Compound 9 4.13 5.88 (0.138, 0.125) Experimental Example 3-10 Compound 10 4.14 5.82 (0.136, 0.125) Experimental Example 3-11 Compound 11 4.13 5.87 (0.137, 0.125) Experimental Examples 3-12 Compound 12 4.15 5.95 (0.136, 0.125) Experimental Example 3-13 Compound 13 4.12 5.98 (0.138, 0.126) Experimental Examples 3-14 Compound 14 4.07 5.91 (0.137, 0.125) Experimental Example 3-15 Compound 15 4.08 5.92 (0.136, 0.127) Experimental Examples 3-16 Compound 16 4.09 5.93 (0.135, 0.127) Comparative Experimental Example 3-1 C1 4.67 5.23 (0.136, 0.127) Comparative Experimental Example 3-2 C2 4.70 5.24 (0.136, 0.127) Comparative Experimental Example 3-3 C3 4.72 5.24 (0.136, 0.127)

As shown in Table 3, the organic light emitting devices of Experimental Examples 3-1 to 3-16 exhibited lower voltage and higher efficiency characteristics than the organic light emitting devices of Comparative Experimental Examples 3-1 to 3-3.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (8)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
L ₁ and L ₂ are each independently a single bond; A halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 40 carbon atoms, and an arylene group having 6 to 40 carbon atoms substituted or unsubstituted with a heteroalkyl group having 1 to 40 carbon atoms and containing at least one of O, N, ; O, N, Si and / or a substituted or unsubstituted C1 to C40 heteroalkyl group containing at least one of a halogen, a nitro group, a cyano group, an alkyl group having 1 to 40 carbon atoms, and O, N, S < / RTI > having from 2 to 60 carbon atoms,
L ₃ is a single bond; Or a substituted or unsubstituted arylene group having 6 to 40 carbon atoms,
Ar ₁ is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, dimethylfluorenyl, methylphenylfluorenyl, diphenylfluorenyl, dibenzofuranyl, or dibenzothiophenyl to be.
The method according to claim 1,
Wherein said compound is represented by the following general formula (2)
compound:
(2)

In Formula 2,
L ₁ , L ₂ , L ₃ and Ar ₁ are the same as defined in claim 1.
The method according to claim 1,
L ₁ and L ₂ are each independently a single bond or an arylene group having 6 to 40 carbon atoms,
compound.
The method according to claim 1,
L ₁ and L ₂ are each independently a single bond or a phenylene group,
compound.
The method according to claim 1,
L ₃ represents a single bond, phenylene, phenanthrenediyl, dimethylfluorenediyl, methylphenylfluorenediyl, diphenylfluorenediyl, phenylene-phenanthrenediyl, phenylene-dimethylfluorenediyl, phenylene-methylphenylfluorene Diyl, or phenylene-diphenylfluorenediyl,
compound.
The method according to claim 1,
Wherein said compound is selected from the group consisting of < RTI ID = 0.0 >
compound:

A first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound according to any one of claims 1 to 6 , An organic light emitting element.
8. The method of claim 7,
Wherein the organic material layer includes a hole transporting layer or an electron blocking layer,
Wherein the hole transporting layer or the electron blocking layer comprises the compound,
Organic light emitting device.

Images