KR20130113357A - New arylcarbazolylacridine-based organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Abstract

PURPOSE: An arylcarbazolylacridine derivative is provided to lower driving voltage when being applied to an organic electroluminescent device and to improve light emitting efficiency, brightness, thermal stability, and lifetime. CONSTITUTION: An acrylcarbazolylacridine derivative is denoted by chemical formula F. The derivative is a material for an organic electroluminescent device. The organic electroluminescent device has one or more organic thin film layers including a light emitting layer between an anode and a cathode. One or more layers among the organic thin film layers contain one or more kinds of the derivatives. The light emitting layer contains the derivative as a phosphorescent green host material or a fluorescent green host material.

Description

Novel arylcarbazolyl acridine-based organic light emitting compound and organic electroluminescent device comprising the same {New arylcarbazolylacridine-based organic electroluminescent compounds and organic electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound and an organic electroluminescent device using the same, and more particularly, can be applied to an organic electroluminescent device as a phosphorescent green host material, a fluorescent green host material, a hole injection layer material, or a hole transport layer material. The present invention relates to a novel arylcarbazolyl acridine-based organic light emitting compound and an organic electroluminescent device comprising the same.

Generally, an organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when a voltage is applied between the two electrodes when the organic layer is positioned between the anode and the cathode, holes are injected into the organic layer and holes are injected into the organic layer. When the injected holes and electrons meet, an exciton is formed. When the exciton falls back to the ground state, light is emitted.

In 1950, Bernanose observed the emission of organic thin films by applying a high alternating voltage to organic thin films. In 1965, an anthracene single crystal was injected with current to generate singlet excitons, ≪ / RTI >

As one method for making an organic electroluminescent device efficiently, research has been conducted to manufacture an organic material layer in a multi-layer structure instead of a single layer. In 1987, Tang presented an organic electroluminescent device in a laminated structure divided into a functional layer of a hole layer and a light emitting layer. Most of the organic electroluminescent devices in use currently receive holes from a substrate, an anode, and optionally an anode. It consists of a hole injection layer, a hole transport layer for selectively transferring holes, a light emitting layer for recombining holes and electrons to emit light, an electron transport layer for selectively transferring electrons, an electron injection layer for receiving electrons from the cathode, and a cathode .

The reason why the EL device is manufactured in multiple layers is that the movement speeds of the holes and the electrons are different. Therefore, if the appropriate hole injection layer, the transfer layer, the electron transfer layer, and the electron injection layer are made, holes and electrons can be effectively transferred. This is because the light emission efficiency can be improved by balancing the holes and the electrons.

Electrons injected from the electron injection layer and holes transferred from the hole injection layer recombine in the emission layer to form excitons, and fall from the singlet excited state to the ground state and are called fluorescence, and fall from the triplet excited state to the base state. Luminescence is called phosphorescence. Theoretically, when the exciton is generated by recombination of carriers in the emission layer, the ratio of singlet and triplet excitons is generated at a ratio of 1: 3. When phosphorescence is used, the internal quantum efficiency can be increased to 100%.

In general, a carbazole ring compound such as CBP (4,4-dicarbazolylbiphenyl) is used as a phosphorescent host material, and a metal complex compound containing a heavy atom such as Ir or Pt is widely used as a phosphorescent guest material.

However, CBP, which is currently used phosphorescent host material, has a low Tg of about 110 ° C. and easily crystallizes in the device, and thus has a very short lifespan of about 150 hours.

The present invention has been made to solve the problems of the prior art, and can be applied to an organic electroluminescent device as a phosphorescent green host material, a fluorescent green host material, a hole injection layer material, or a hole transport layer material, and an organic electroluminescent device When applied to the aryl carbazolyl acrydine derivatives that can lower the driving voltage, improve the luminous efficiency, brightness, thermal stability and device life, and provides an organic electroluminescent device having high efficiency and long life characteristics using the same For the purpose of

According to the present invention,

It provides an arylcarbazolyl acridine-based derivative represented by the following formula (F):

Formula F]

Where

R 1, R 2 and R 3 are each independently a hydrogen atom, a C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ group;

Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이며,

,

,

,

,

,

or

Is,

K and L are each independently a nitrogen atom or a carbon atom, and K and L are not the same atom;

A, B, C, D and E are each independently C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ groups;

Small and small atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, tria unsubstituted or substituted with one or more substituents selected from the group Sol, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이거나;

,

,

,

,

,

or

;

Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환된 6~30의 아릴기 또는 5~60의 헤테로아릴기이며,

,

,

,

,

,

or

6 to 30 aryl groups or 5 to 60 heteroaryl groups substituted with one or more substituents selected from the group consisting of

When K is a nitrogen atom, one of A and B is absent, and when L is a nitrogen atom, one of C and D is absent;

O, P, Q and R are carbon atoms or absent, where when O, P, Q and R are absent R3 is also absent;

R 4 and R 5 are each independently a hydrogen atom, C 1 -C 10 straight or branched chain alkyl, or C 1 -C 10 linear or branched alkoxy group;

X 1, X 2, X 3 and X 4 are each independently a carbon atom, a nitrogen atom or a sulfur atom;

Y1, Y2, Y3, and Y4 are each independently a carbon atom, a nitrogen atom, or a sulfur atom.

Further, according to the present invention,

In the organic electroluminescent element in which the organic thin film layer which consists of one layer or multiple layers containing a light emitting layer at least is clamped between a cathode and an anode,

At least one or more of the organic thin film layers provides an arylcarbazolyl acridine derivative of the present invention alone or in combination of two or more.

In addition, the organic light emitting compound and the organic light emitting device using the same according to the present invention is based on the organic light emitting compound corresponding to the formula 1 to 332.

The arylcarbazolyl acridine derivative of the present invention can be applied to an organic electroluminescent device as a phosphorescent green host material, a fluorescent green host material, a hole injection layer material, or a hole transport layer material, and is driven when applied to an organic electroluminescent device. The voltage can be lowered, and the luminous efficiency, luminance, thermal stability and device life can be improved.

In addition, the organic electroluminescent device employing the arylcarbazolyl acridine derivative has high efficiency and long life.

Hereinafter, the present invention will be described in detail.

The present invention may be modified in various ways and may have various forms, and thus embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, the term " comprising " or " consisting of ", or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

The present invention relates to an arylcarbazolyl acridine derivative represented by the following formula (F):

Formula F]

Where

R 1, R 2 and R 3 are each independently a hydrogen atom, a C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ group;

Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이며,

,

,

,

,

,

or

Is,

K and L are each independently a nitrogen atom or a carbon atom, and K and L are not the same atom;

A, B, C, D and E are each independently C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ groups;

Small and small atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, tria unsubstituted or substituted with one or more substituents selected from the group Sol, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이거나;

,

,

,

,

,

or

;

Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환된 6~30의 아릴기 또는 5~60의 헤테로아릴기이며,

,

,

,

,

,

or

6 to 30 aryl groups or 5 to 60 heteroaryl groups substituted with one or more substituents selected from the group consisting of

When K is a nitrogen atom, one of A and B is absent, and when L is a nitrogen atom, one of C and D is absent;

O, P, Q and R are carbon atoms or absent, where when O, P, Q and R are absent R3 is also absent;

R 4 and R 5 are each independently a hydrogen atom, C 1 -C 10 straight or branched chain alkyl, or C 1 -C 10 linear or branched alkoxy group;

X 1, X 2, X 3 and X 4 are each independently a carbon atom, a nitrogen atom or a sulfur atom;

Y1, Y2, Y3, and Y4 are each independently a carbon atom, a nitrogen atom, or a sulfur atom.

In the arylcarbazolyl acridine derivative of the present invention, more preferably, the aryl group of 6 to 30 or the heteroaryl group of 5 to 60 is phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyri Diyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, Dehydroindole,

,

,

,

,

,

또는

로 이루어진 군으로부터 선택되며;

,

,

,

,

,

or

≪ / RTI >

R 4 and R 5 are each independently a hydrogen atom, a straight or branched chain alkyl of C 1 to C 5 or a straight or branched chain alkoxy group of C 1 to C 5;

X 1, X 2, X 3 and X 4 are each independently a carbon atom, a nitrogen atom or a sulfur atom;

Y1, Y2, Y3, and Y4 may each independently be a carbon atom, a nitrogen atom, or a sulfur atom.

In the arylcarbazolyl acridine derivative of the present invention, still more preferably,

R 1, R 2 and R 3 are each independently a hydrogen atom or a C 1 -C 10 straight or branched chain alkyl, phenyl, naphthyl, pyridinyl or pyrimidinyl group;

A, B, C, D and E are each independently a C1-C10 straight or branched alkyl group;

Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole, benzoxa, unsubstituted or substituted with one or more deuterium atoms Sol, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이거나;

,

,

,

,

,

or

;

Phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl, pyridinyl and pyrimidinyl groups Dazinyl, triazinyl, imidazole, triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

또는

이거나;

,

,

,

,

,

or

;

Phenyl, pyridinyl, pyrimidinyl or triazinyl substituted with one or more substituents selected from the group consisting of;

When K is a nitrogen atom, one of A and B is absent, and when L is a nitrogen atom, one of C and D is absent;

O, P, Q and R are carbon atoms or absent, where when O, P, Q and R are absent, R3 is also absent;

R4 and R5 are each independently a C1-C5 linear or branched alkyl group;

X 1, X 2, X 3 and X 4 are each independently a carbon atom or a nitrogen atom;

Y1, Y2, Y3, and Y4 may each independently be a carbon atom or a nitrogen atom.

The arylcarbazolyl acridine derivative of the present invention can be usefully used as a material for an organic electroluminescent device, and in particular, a phosphorescent green host material, a fluorescent green host material, a hole injection layer material, or a hole in an organic electroluminescent device material. It can be usefully used as a transport layer material.

The arylcarbazolyl acridine derivatives of the present invention may specifically have a structure of the following Chemical Formulas 1 to 332 (hereinafter, the chemical formulas are omitted and are not limited thereto).

The present invention also relates to

In the organic electroluminescent element in which the organic thin film layer which consists of one layer or multiple layers containing a light emitting layer at least is clamped between a cathode and an anode,

At least one layer of the said organic thin film layer is related with the organic electroluminescent element characterized by containing the arylcarbazolyl acridine type derivative of this invention individually by 1 type or in combination of 2 or more types.

The arylcarbazolyl acridine-based derivative exhibits excellent characteristics when the phosphorescent green host material or the fluorescent green host material is contained in the emission layer of the organic thin film layer.

In addition, when the organic thin film layer includes a hole injection layer, when the arylcarbazolyl acridine derivative is contained in the hole injection layer as a hole injection layer material, excellent characteristics are exhibited.

In addition, when the organic thin film layer includes a hole transport layer, the arylcarbazolyl acridine-based derivative exhibits excellent characteristics when the hole transport layer is contained as a hole transport layer material.

The organic electroluminescent device is

The anode, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode may have a stacked structure in this order.

Hereinafter, the organic electroluminescent element of the present invention will be described by way of example. However, the contents illustrated below do not limit the organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL) and / or a hole transport layer (HTL), an emission layer (EML), and a cathode (electron injection electrode) are sequentially stacked. Preferably, it may further include an electron blocking layer (EBL) between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) between the cathode and the light emitting layer. have.

In the method of manufacturing an organic electroluminescent device according to the present invention, first, a positive electrode is coated on a surface of a substrate by a conventional method to form a positive electrode. At this time, the substrate to be used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.

Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating using a conventional method. As the hole injection layer material, the arylcarbazolyl acridine derivative of the present invention may be preferably used. Other hole injection layer materials include copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3- Methylphenylamino) triphenylamine (m-MTDATA), 4,4 ', 4 "-tris (3-methylphenylamino) phenoxybenzene (m-MTDAPB), starburst amines 4,4', 4 "-Tri (N-carbazolyl) triphenylamine (TCTA), 4,4 ', 4" -tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA) or An example is the IDE406, available from Idemitsu.

A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer by a conventional method to form a hole transport layer. In this case, the arylcarbazolyl acridine derivative of the present invention may be preferably used as the hole transport layer material, and bis (N- (1-naphthyl-n-phenyl)) benzidine (α-) as another hole transport layer material. NPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl-benzidine (NPB) or N, N'-diphenyl-N, N'-bis (3-methylphenyl)- 1,1'- diphenyl-4,4'- diamine (TPD) is mentioned.

A light emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal deposition or spin coating using a conventional method. In this case, as the phosphorescent host material or the fluorescent host material, the arylcarbazolyl acridine derivative of the present invention may be preferably used as the phosphorescent host material. In addition, tris (8-hydroxyquinolinolato) aluminum may be used. (Alq3) can be used, in the case of blue Balq (8-hydroxyquinolineberyllium salt), DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl) Spiro substance, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benz) Oxazolyl) -phenol lithium salts), bis (diphenylvinyl) benzene, aluminum-quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole, and the like.

Fluorescent dopants that can be used with a luminescent fluorescent green host in the emissive layer material are IDE102, IDE105, which is available from Idemitsu, and phosphorus dopant is tris (2-phenylpyridine) iridium (III) (Ir (ppy). 3), iridium (III) bis [(4,6-difluorophenyl) pyridinato-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Lett., 2001, 79, 3082-3084], platinum (II) octaethyl porphyrin (PtOEP), TBE002 (Kobiion Co.) and the like can be used.

An electron transport layer (ETL) material is formed on the surface of the light emitting layer by vacuum thermal deposition or spin coating using a conventional method. At this time, as the electron transport layer material used may be tris (8-hydroxyquinolinolato) aluminum (Alq 3) and the like.

Alternatively, by further forming a hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant together with the light emitting layer, it is possible to prevent the phenomenon that the triplet excitons or holes are diffused into the electron transporting layer.

The hole blocking layer can be formed by vacuum thermal deposition and spin coating using a hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, there is no particular limitation, but (8-hydroxyquinolinolato Lithium biphenoxide (BAlq), bathocuproine (BCP), LiF, etc. may be used as the lithium salt (Li), bis (8-hydroxy-2-methylquinolinonato)

An electron injection layer (EIL) material is formed on the surface of the electron transport layer by vacuum thermal deposition or spin coating using a conventional method. In this case, the material of the electron injection layer to be used is not particularly limited, and preferably materials such as LiF, Liq, Li2O, BaO, NaCl, and CsF can be used.

Finally, a negative electrode is formed on the surface of the electron injecting layer by vacuum thermal deposition using a conventional method.

At this time, as the negative electrode material to be used, lithium, aluminum, aluminum-lithium, calcium, magnesium, (Mg-Ag) or the like may be used. In the case of the front emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode through which light can pass.

The organic electroluminescent device according to the present invention may be manufactured in the same order as described above, that is, in the order of anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode, and vice versa. The electron injection layer, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer and the anode may be manufactured in the order.

Hereinafter, a method for synthesizing the compounds of the present invention will be described below with a representative example. However, the method of synthesizing the compounds of the present invention is not limited to the methods illustrated below, and the compounds of the present invention may be prepared by the methods illustrated below and methods known in the art.

Preparation of Compound [10]

Synthesis of Intermediate Compound [10-6]

[Reaction Scheme 1]

Preparation of Intermediate Compound [10-1]

To the 5 L reaction flask, 200 g (1.368 mol) of alpha-tetrarone, 305.7 g (1.368 mol) of 4-bromophenylhydrazine chloride, and 30 mL of acetic acid are added, followed by stirring in nitrogen atmosphere with 3 L of ethanol. The mixture was heated to reflux for 4 hours and then cooled to room temperature. The resulting solid was filtered and dried to prepare 326 g (80%) of the intermediate compound [23-1].

Preparation of Intermediate Compound [10-2]

Intermediate Compounds [10-1] 320 g (1.07 mol) and 342 g (1.39 mol) of tetrachloro-1,4-benzoquinone are stirred under reflux with 2.5 L of xylene for 4 hours under a nitrogen atmosphere. After cooling to room temperature, an organic layer was separated by adding 2 L of 10% aqueous sodium hydroxide solution to the reaction solution. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The concentrate was recrystallized from ethanol to prepare 280 g (88%) of the intermediate compound [10-2].

Preparation of Intermediate Compound [10-3]

Intermediate Compound [10-2] 280 g (0.945 mol), iodobenzene 964 g (4.727 mol), copper powder 60 g (0.945 mol) and potassium carbonate 195.9 g (1.418 mol) were stirred under reflux with 1.5 L of dimethylformamide for 12 hours. do. The reaction solution is cooled to room temperature and the organic layer is separated with ethyl acetate and saturated salts. The organic layer was collected, dried and recrystallized with methanol to prepare 185 g (53%) of an intermediate compound [10-3].

Preparation of Intermediate Compound [10-4]

180 g (0.484 mol) of intermediate compound [10-3], 65.4 g (0.484 mol) of 2-aminoacetophenone, 30.7 g (0.484 mol) of copper powder, 100.3 g (0.726 mol) of potassium carbonate, and 2 L of phenyl ether Put in a nitrogen atmosphere and stirred for 24 hours at 180 ℃. After completion of the reaction, the reaction solution is filtered using diatomaceous earth. To the filtrate was added 3 L of methanol to solidify. The solid was filtered and separated and purified through column chromatography to prepare 125 g (60%) of an intermediate compound [10-4] as a yellow solid.

Preparation of Intermediate Compound [10-5]

120 g (0.281 mol) of an intermediate compound and 1 L of anhydrous tetrahydrofuran were added to the reaction flask at room temperature. 187 mL (0.562 mol) of methylmagnesium chloride (3.0M) was slowly added dropwise in a nitrogen atmosphere at 0 ° C., and the mixture was stirred at room temperature for 12 hours. After the reaction is completed, the reaction solution is poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. 95 g (76%) of an intermediate compound [10-5] as a white solid was prepared by separation and purification by column chromatography after separation of the organic layer.

Preparation of Intermediate Compound [10-6], [10-7]

95 g (0.215 mol) of an intermediate compound [10-5] are stirred and dissolved in 1 L of dichloromethane in a reaction flask. Add 41.8 mL (0.644 mol) of methanesulfonic acid in a nitrogen atmosphere and stir at room temperature. After completion of the reaction, the reaction solution was slowly added to the water and stirred, followed by extraction with ethyl acetate. The organic layer was separated and purified by column chromatography to prepare 45 g (49%) of an intermediate compound [10-6] and 15 g (16%) of an intermediate compound [10-7].

Preparation of Compound [10]

Dissolve 5.0 g (11.78 mmol) of intermediate compound [10-6] with 100 mL of anhydrous dimethylformamide and slowly add 771 mg (17.67 mmol) of sodium hydride (55%) at 0 ° C. At the same temperature, 3.15 g (11.78 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine are added slowly. After stirring for 3 hours at room temperature, the reaction solution is poured into purified water. The resulting solid is filtered, dissolved in dichloromethane and passed through silica gel. The filtrate was recrystallized from methanol to prepare 4.5g (58%) of the target compound [10].

Synthesis Examples 1 to 332: Synthesis of arylcarbazolyl acridine derivative

According to the method of Reaction Example 1, the compound of Compounds 1 to 332 of the present invention was prepared, and the result of the confirmation is shown in the following [Table 1].

[First group (group)]

Comparative Example 1: Fabrication of Organic Electroluminescent Device

Using a compound represented by the formula (a) as a phosphorescent green host, using a compound represented by the formula (c) as a phosphorescent green dopant, 2-TNATA (4,4 ', 4 ”-tris (N-naphthalen-2- yl) -N-phenylamino) -triphenylamine) is used as the hole injection layer material, and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) is used as the hole transport layer material. Thus, an organic electroluminescent device having the following structure was produced: ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / Compound a + Compound c (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm ² (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm, ultrasonically cleaned in acetone isopropyl alcohol and pure water for 15 minutes, and then UV ozone cleaning for 30 minutes. Was used. 2-TNATA was vacuum-deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On the hole injection layer, α-NPD was vacuum-deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by Chemical Formula a and a compound represented by Chemical Formula c (10% doping) were vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injection layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic electroluminescent device as shown in Table 3 below. This is referred to as Comparative Sample 1.

Comparative Example 2: Fabrication of Organic Electroluminescent Device

Using a compound represented by the formula b as a phosphorescent green host, using a compound represented by the formula c as a phosphorescent green dopant, 2-TNATA (4,4 ', 4 ”-tris (N-naphthalen-2- yl) -N-phenylamino) -triphenylamine) is used as the hole injection layer material, and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) is used as the hole transport layer material. Thus, an organic electroluminescent device having the following structure was fabricated: ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / Compound b + Compound c (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm ² (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm, ultrasonically cleans for 15 minutes in acetone, isopropyl alcohol and pure water, and then UV ozone for 30 minutes. It was used by washing. 2-TNATA was vacuum-deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On the hole injection layer, α-NPD was vacuum-deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by Formula b and a compound represented by Formula c (10% doping) were vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injection layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic electroluminescent device as shown in Table 3 below. This is called Comparative Sample 2.

Examples 1 to 332: Fabrication of Organic Electroluminescent Device

In Comparative Example 1, ITO was prepared in the same manner as in Comparative Example 1, except that compounds represented by Chemical Formulas 1 to 332 disclosed in Synthesis Example were used as emission layer phosphorescent green host compounds instead of compound a as emission layer phosphorescent green host compounds. / 2-TNATA (80 nm) / α-NPD (30 nm) / [phosphorescent green host compound 1 to 332 + compound c (10%)] (30 nm) / Alq ₃ (30 nm) / LiF (0.5 An organic electroluminescent device having a structure of nm) / Al (60 nm) was prepared. These are referred to as Samples 1 to 332, respectively.

Evaluation Example 1: Evaluation of Luminescence Characteristics of Comparative Samples 1 and 2 and Samples 1 to 332

With respect to the comparison samples 1, 2 and Sample 1 ~ 332, Keithley sourcemeter "2400 ", KONIKA MINOLTA using the "CS-2000" respectively evaluate the luminescence brightness and luminescence efficiency, the luminescence peak, and the results [Second pyogun (Iii)] . The samples showed green emission peaks in the range of 513-524 nm.

[Second group (group)]

As shown in [Second Table], Samples 1 to 332 showed improved light emission characteristics compared to Comparative Samples 1 and 2.

Evaluation Example 2 Evaluation of Life Characteristics of Comparative Samples 1 and 2 and Samples 1 to 332

For Comparative Samples 1 and 2 and Samples 1 to 332, the ENC technology LTS-1004AC Life Time Measuring Device was used to measure the time at which the life reached 97% based on 3500 nit, and evaluated the results. 3 group].

[Third Table]

As shown in Table 4, Samples 1 to 332 showed improved life characteristics compared to Comparative Samples 1 and 2.

Claims (8)

Arylcarbazolyl acridine derivatives represented by the following formula (F):
Formula F]

In this formula,
R 1, R 2 and R 3 are each independently a hydrogen atom, a C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ group;
Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

Is,
K and L are each independently a nitrogen atom or a carbon atom, and K and L are not the same atom;
A, B, C, D and E are each independently C 1 -C 10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , or Si (C ₆ H ₅ ) ₃ groups;
Small and small atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, tria unsubstituted or substituted with one or more substituents selected from the group Sol, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

;
Deuterium atom, C1-C10 straight or branched chain alkyl, halogen, nitrile, CF ₃ , Si (CH ₃ ) ₃ , Si (C ₆ H ₅ ) ₃ , phenyl, naphthyl, pyridinyl and pyrimidinyl groups Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole unsubstituted or substituted with one or more substituents selected from , Benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

6 to 30 aryl groups or 5 to 60 heteroaryl groups substituted with one or more substituents selected from the group consisting of
When K is a nitrogen atom, one of A and B is absent, and when L is a nitrogen atom, one of C and D is absent;
O, P, Q and R are carbon atoms or absent, where when O, P, Q and R are absent R3 is also absent;
R 4 and R 5 are each independently a hydrogen atom, C 1 -C 10 straight or branched chain alkyl, or C 1 -C 10 linear or branched alkoxy group;
X 1, X 2, X 3 and X 4 are each independently a carbon atom, a nitrogen atom or a sulfur atom;
Y1, Y2, Y3, and Y4 are each independently a carbon atom, a nitrogen atom, or a sulfur atom. The method according to claim 1,
The aryl group of 6 to 30 or the heteroaryl group of 5 to 60 is phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole , Triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

≪ / RTI >
R 4 and R 5 are each independently a hydrogen atom, a straight or branched chain alkyl of C 1 to C 5 or a straight or branched chain alkoxy group of C 1 to C 5;
X 1, X 2, X 3 and X 4 are each independently a carbon atom, a nitrogen atom or a sulfur atom;
The Y1, Y2, Y3, Y4 are each independently an arylcarbazolyl acridine derivative, characterized in that the carbon atom, nitrogen atom or sulfur atom. The method according to claim 1,
R 1, R 2 and R 3 are each independently a hydrogen atom or a C 1 -C 10 straight or branched chain alkyl, phenyl, naphthyl, pyridinyl or pyrimidinyl group;
A, B, C, D and E are each independently a C1-C10 straight or branched alkyl group;
Phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, triazole, benzoxa, unsubstituted or substituted with one or more deuterium atoms Sol, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

;
Phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl, pyridinyl and pyrimidinyl groups Dazinyl, triazinyl, imidazole, triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, dihydroindole,

,

,

,

,

,

or

;
Phenyl, pyridinyl, pyrimidinyl or triazinyl substituted with one or more substituents selected from the group consisting of;
When K is a nitrogen atom, one of A and B is absent, and when L is a nitrogen atom, one of C and D is absent;
O, P, Q and R are carbon atoms or absent, where when O, P, Q and R are absent, R3 is also absent;
R4 and R5 are each independently a C1-C5 linear or branched alkyl group;
X 1, X 2, X 3 and X 4 are each independently a carbon atom or a nitrogen atom;
Y 1, Y 2, Y 3 and Y 4 are each independently an arylcarbazolyl acridine derivative, characterized in that the carbon atom or nitrogen atom. The method according to claim 3,
The arylcarbazolyl acridine derivative is any one of compounds 1 to 332 aryl carbazolyl acridine derivatives:

The method according to claim 1,
The arylcarbazolyl acridine derivative is an organic electroluminescent device material. The method according to claim 5,
The arylcarbazolyl acridine derivative is an phosphorescent green host material, a fluorescent green host material, a hole injection layer material or a hole transport layer material of the organic electroluminescent device material. In the organic electroluminescent element in which the organic thin film layer which consists of one layer or multiple layers containing a light emitting layer at least is clamped between a cathode and an anode,
At least one or more layers of the organic thin film layer contain the arylcarbazolyl acridine derivatives of claim 1 alone or in combination of two or more. The method of claim 7,
And the arylcarbazolyl acridine derivative is contained in the light emitting layer of the organic thin film layer as a phosphorescent green host material or a fluorescent green host material.