KR101282176B1 - Chemical and Organic Electronic Element using the same, Electronic Device thereof - Google Patents

Abstract

The present invention provides a compound, an organic electric device using the same, and an electronic device thereof.

Description

Compound and organic electronic device using same, and electronic device thereof {Chemical and Organic Electronic Element using the same, Electronic Device about}

The present invention relates to a compound, an organic electronic device using the same, and an electronic device thereof.

All.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer may have a multi-layer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

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

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

In another aspect, the present invention provides an organic electronic device and an electronic device including the compound represented by the above formula.

The present invention is a novel compound, which is useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc. Provides a useful effect as a transport material.

The present invention provides an effect of increasing the efficiency of the organic electronic device, lowering the driving voltage, increasing the lifetime and stability.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

The present invention is a compound represented by the following formula (1) or (2).

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; A C ₁ to C ₅₀ alkyl group; C ₅ -C ₆₀ aryl group; It may be a hetero atom group of C ₃ ~ C ₅₀ containing at least one hetero atom, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), but is not limited thereto. In this case, n and m may be an integer of 1 to 4.

In this case, R ₁ , R ₂ , R ₃ and R ₄ may be bonded to adjacent groups to form a saturated or unsaturated ring. For example, R ₂ and R ₃ , R ₂ and R ₄ , R ₃ and R ₄ may combine with each other to form a saturated or unsaturated ring.

L is a single bond; Halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkyl group, C ₈ ~ A C ₅ to C ₆₀ arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of C ₂₀ arylalkenyl groups, C ₅ to C ₂₀ heterocyclic groups, nitrile groups and acetylene groups; A halogen group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₅ ~ C ₂₀ of the heterocyclic group, a nitrile group and in the group consisting of acetylene with one or more substituents being unsubstituted or substituted with O, N, S It may be a C ₄ ~ C ₅₀ Heteroarylene group having a but is not limited thereto. In addition, l may be an integer of 0 to 2 and o may be an integer of 1 to 2.

Ar ₁ and Ar ₂ are each independently C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ Alkenyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ Aryl group, C ₈ ~ C ₂₀ A C ₁ -C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of an arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₅ -C ₂₀ heterocyclic group, nitrile group and acetylene group; Halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C C unsubstituted or substituted with one or more groups selected from the group consisting of an aryl group of ₆ to C ₂₀ , an aryl alkenyl group of C ₈ to C ₂₀ , a silane group, a boron group, a germanium group and a heterocyclic group of C ₅ to C ₂₀ Aryl groups of ₆ to C ₂₀ ; A halogen group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₂₀ aryl group, C ₈ Or an unsubstituted or substituted with one or more substituents from the group consisting of an arylalkyl group of ~ C _20, an arylalkenyl group of C ₈ ~ C ₂₀ , a heterocyclic group of C ₅ ~ C ₂₀ , a nitrile group, and an acetylene group Substituted or unsubstituted C _{3 Through} C _{50 It} may be a heteroaryl group, but is not limited thereto.

At this time, the aryl group, heteroaryl group of Ar ₁ , Ar ₂ may be represented as follows, but is not limited thereto.

As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1- anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group , 4-phenanthryl group, 1-phenalinyl group, 2-phenalylyl group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenyl Aryl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3 -Yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group , 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 ”-t-butyl-p-terphenyl-4-yl group, fluorenyl group, etc. are mentioned. 2-pyrrolyl group, 3-pyrrolyl group, 2-pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indole Reel group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-phosphorus Reel group, 1-isoindoleyl group, 3-isoindoleyl group, 4-isoindoleyl group, 5-isoindoleyl group, 6-isoindoleyl group, 7-isoindoleyl group, 2-furyl group, 3 -Furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-iso Benzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl Group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carba Sleepyl group, 3-carbazolyl group, 4-carbazolyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4 -Acridinyl, 9-acridinyl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1 , 10-phenanthroline-5- diary, 1-phenazine yl, 2-phenazine yl, 1-phenothiazine yl, 2-phenothiazine yl, 3-phenothiazine yl, 4-phenothiazine yl , 1-phenoxazinediyl, 2-phenoxazinediyl, 3-phenoxazinediyl, 4-phenoxazinediyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group, 2-t-butyl Pyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl 3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group And 4-t-butyl-3-indolyl group.

In the above formula, the hetero ring group is a heterocyclic group containing O, N or S as a hetero atom, carbon number is not particularly limited, but may be 2-60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzoxazole group, a benzthiophene group, a dibenzothiophene group, a benzfuranyl group, But are not limited to these.

In this case, the substituents may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring or ring, for example, an aliphatic, aromatic, or heteroaromatic monocyclic or polycyclic ring.

According to another exemplary embodiment of the present invention, the present invention may include two or more structures of Formula 1 or 2.

Meanwhile, the compound having the structural formula may be used in a solution process. In other words, the compound may form an organic material layer of an organic electric device, which will be described later, by a soluble process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

The compound represented by Chemical Formula 1 or 2 may be represented by dividing into Chemical Formulas 3 to 6 according to the type of substituents.

In Formulas 3 to 6, R ₁ to R ₄ and Ar ₁ , Ar ₂ , and L may be the same as those of Formulas 1 and 2 described above.

Meanwhile, the compounds represented by Formulas 1 to 6 may each be one or more than one of the compounds represented by Formula 7.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, preparation examples or synthesis examples of the compounds belonging to Chemical Formulas 1 to 7 will be described.

However, some of the compounds belonging to the general formula 1 to 7 because of the large number of compounds belonging to the general formula (1) 7 will be described by way of example. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.

Hereinafter, the compounds were synthesized according to the synthesis method described above, and the examples in which the compounds were applied to an organic material layer of an organic electroluminescent device, for example, an organic electroluminescent device, were compared with those of commonly used compounds.

Synthesis of Intermediate 1

[Reaction Scheme 1]

2-bromofluorene was dissolved in a benzene solvent under nitrogen, and N- bromosuccinimide was added and refluxed for 5 hours. At the end of the reaction, the reaction was cooled to room temperature and succinimide was removed by vacuum filtration. The product obtained by concentrating the organic solvent was recrystallized using a benzene solvent to obtain the desired intermediate 1 (yield: 61%).

Synthesis of Intermediate 2

[Reaction Scheme 2]

The intermediate 1 and PPh ₃ synthesized in the above step under nitrogen were dissolved in a benzene solvent and refluxed for 12 hours. When the reaction was terminated, the temperature of the reactant was lowered, and the resulting precipitate was filtered under reduced pressure and then washed with ether to obtain the desired intermediate 2 (61%).

Synthesis of Intermediate 3

Scheme 3

The intermediate 2 and KO t Bu synthesized in the above step under nitrogen were dissolved in THF solvent, and then stirred at room temperature for 30 minutes. Then paraformaldehyde was added and stirred at 30 ℃ for 12 hours. After the reaction was completed, hexane was added, and the resultant was filtered under reduced pressure using silica-gel, followed by wiping with CH ₂ Cl ₂ . The resulting product by concentrating the organic solvent was separated using column chromatography to give the desired intermediate 3 (yield: 93%).

Synthesis of Intermediate 4

[Reaction Scheme 4]

Diphenylmethane was dissolved in THF solvent under nitrogen, and n-BuLi was slowly added thereto at 0 ° C.

After stirring at room temperature for 30 minutes, 2-bromofluorenone was added and stirred at room temperature for 6 hours.

After the reaction was terminated, ammonium chloride aqueous solution was added and extracted with CH ₂ Cl ₂ . After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate 4 (yield: 93%).

Synthesis of Intermediate 5

Scheme 5

Intermediate 4 and p -toluenesulphonic acid synthesized in the above step under nitrogen were dissolved in toluene solvent and refluxed for 4 hours through Dean-Stark trap. After the reaction was completed, the temperature of the reactant was lowered to room temperature, NaHCO ₃ aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate 5 (yield: 90%).

Synthesis of Intermediate 6

[Reaction Scheme 6]

Intermediate 1, 9-bromofluorene, and KOH synthesized in the above step were dissolved in a solvent mixed in a ratio of DMSO: MeOH = 8: 2 and stirred for 30 minutes. After adding acetic acid and stirring for 10 minutes, the reaction was poured into water. The precipitate thus formed was filtered under reduced pressure, and then the desired intermediate 6 was obtained through recrystallization using benzene and an ether solvent (yield: 78%).

Synthesis of intermediate A

[Reaction Scheme 7]

Carbazole was dissolved in CH ₂ Cl ₂ solvent under nitrogen, N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH ₂ Cl ₂ and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH ₂ Cl ₂ and methanol solvent to obtain the desired intermediate A (yield: 83%).

Synthesis of intermediate B

[Reaction Scheme 8]

Intermediate A, iodobenzene, copper powder, 18-crown-6, K ₂ CO ₃ synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate B (yield: 80%).

Synthesis of intermediate C

Scheme 9

Intermediate A, 1-iodonaphthalene, copper powder, 18-crown-6, K ₂ CO ₃ synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate C (yield: 78%).

Synthesis of intermediate D

[Reaction Scheme 10]

Intermediate A, 2-iodonaphthalene, copper powder, 18-crown-6, K ₂ CO ₃ synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate D (yield: 79%).

Synthesis of intermediate E

[Reaction Scheme 11]

Intermediate A, 4-iodobiphenyl, copper powder, 18-crown-6, K ₂ CO ₃ synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate E (yield: 77%).

Synthesis of Intermediate F

[Reaction Scheme 12]

Intermediate B synthesized in the above step was dissolved in anhydrous THF (tetrahydrofuran), and the temperature of the reactant was lowered to 78 ° C. After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour. Then, the temperature of the reaction was lowered to 78 ℃, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate F (yield: 73%).

Synthesis of Intermediate G

[Reaction Scheme 13]

The intermediate E synthesized in the above step was dissolved in anhydrous THF, and the temperature of the reaction was lowered to -78 ° C.

After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour.

Then, the temperature of the reaction was lowered to -78 ℃, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ .

After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate G (yield: 74%).

Synthesis of Intermediate H

[Reaction Scheme 14]

Intermediate F, 4-bromoaniline, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in the above step were dissolved in THF and H ₂ O, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate H (yield: 64%).

Synthesis of Intermediate I

[Reaction Scheme 15]

The intermediate G, 4-bromoaniline, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ synthesized in the above step were dissolved in THF and H ₂ O, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate I (yield: 62%).

Synthesis of Intermediate J

[Reaction Scheme 16]

Intermediate C and aniline, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate J (yield: 76%).

Synthesis of Intermediate K

[Reaction Scheme 17]

Intermediate D, 9-aminophenanthrene, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent.

After filtration under reduced pressure, the resultant organic solvent was concentrated and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate K (yield: 69%).

Synthesis of Intermediate L

[Reaction Scheme 18]

The intermediate H synthesized in the above step and 4-iodobiphenyl, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu were dissolved in a toluene solvent and stirred at 80 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent.

After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate L (yield: 54%).

Synthesis of Intermediate M

Scheme 19

The intermediate I and iodobenzene, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 80 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent.

After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate M (yield: 60%).

Synthesis of Compound 1

[Reaction Scheme 20]

Intermediate J and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step was dissolved in a toluene solvent, and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 1 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 60%).

Synthesis of Compound 2

Scheme 21

The intermediate J and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 2 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 58%).

Synthesis of Compound 3

[Reaction Scheme 22]

The intermediate J and the intermediate 6, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 3 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).

Synthesis of Compound 61

[Reaction Scheme 23]

The intermediate K and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 61 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).

Synthesis of Compound 62

Scheme 24

The intermediate K and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 62 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 49%).

Synthesis of Compound 63

[Reaction Scheme 25]

The intermediate K and the intermediate 6, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 63 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 42%).

Synthesis of Compound 88

[Reaction Scheme 26]

The intermediate L and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 88 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 81%).

Synthesis of Compound 89

[Reaction Scheme 27]

The intermediate L and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 89 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 79%).

Synthesis of Compound 90

[Reaction Scheme 28]

The intermediate L and the intermediate 6, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 90 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 77%).

Synthesis of Compound 121

[Reaction Scheme 29]

Intermediate M and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 121 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 83%).

Synthesis of Compound 122

[Reaction Scheme 30]

Intermediate M and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 122 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 80%).

Synthesis of Compound 123

[Reaction Scheme 31]

Intermediate M and the intermediate 6, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 123 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 73%).

Synthesis of Intermediate N

[Reaction Scheme 32]

Intermediate F, 1,3,5-tribromobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in the above step were dissolved in THF and H ₂ O solvents and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate N (yield: 59%).

Synthesis of Intermediate O

[Reaction Scheme 33]

Intermediate N, aniline, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate O (yield: 43%).

Synthesis of Compound 163

[Reaction Scheme 34]

The intermediate O synthesized in the above step and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu was dissolved in a toluene solvent, and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 163 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 51%).

Synthesis of compound 164

[Reaction Scheme 35]

Intermediate O and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 164 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 46%).

Synthesis of Compound 165

[Reaction Scheme 36]

Intermediate O and the intermediate 6, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 165 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 41%).

Synthesis of Intermediate P

[Reaction Scheme 37]

The intermediate B synthesized in the above step under nitrogen was dissolved in a solvent of CH ₂ Cl ₂ , and then N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH ₂ Cl ₂ and washed with water.

After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH ₂ Cl ₂ and methanol solvent to obtain the desired intermediate P (yield: 90%).

Synthesis of Intermediate Q

[Reaction Scheme 38]

The intermediate P and aniline, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate Q (yield: 83%).

Synthesis of Compound 175

[Reaction Scheme 39]

Intermediate Q and the intermediate 3, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 175 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 66%).

Synthesis of Compound 176

[Reaction Scheme 40]

The intermediate Q and the intermediate 5, Pd ₂ (dba) ₃ , P (tBu) ₃ and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 176 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 62%).

Synthesis of Compound 177

[Reaction Scheme 41]

Synthesis of Other Compounds

Synthesis of other compounds is substantially the same as the method for synthesizing compounds that specifically describes the preparation examples, except that some of the starting materials or intermediates are replaced with starting materials or intermediates of the corresponding compounds.

For example, the synthesis of the chemicals 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, in the intermediate J, instead of phenyl at the N atom of the amine group, naphthyl or biphenyl group, Synthesis method is substantially the same as that of Compound 1 except that Intermediate 3, which is substituted with an anthryl group, a carbazole group, a fluorene group, and the like are reacted. Synthesis of chemicals 40, 43, 46, 49, 53, 55, 58 replaces the naphthyl group, biphenyl group, anthryl group, carbazole group, fluorene group, etc. instead of phenyl in N atom of amine group in intermediate J. And the method of synthesis is substantially the same as that of compound 1, except that the intermediate of the naphthyl group of the N atom of carbazole reacts with intermediate 3.

Likewise, the method for synthesizing other compounds is the same except that the above-described examples and starting materials or intermediates are replaced with the corresponding compounds, and methods for synthesizing other compounds form part of the present specification.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing a substituent used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electronic device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.

The compound according to the present invention can be used in various applications in the organic light emitting electronic device according to the type and nature of the substituent.

The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic material layer is formed using the above-described compounds.

When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of an organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

Organic electroluminescent devices in which the compounds of the present invention can be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.

As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic light emitting diode (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.

Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

The organic light emitting device according to another embodiment of the present invention, except that at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.

Although not shown, the organic light emitting diode further includes a hole blocking layer (HBL) that blocks hole movement, an electron blocking layer (EBL) that blocks electrons from moving, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.

Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited 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, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated 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, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.

The organic light emitting device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention 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), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

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

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.

Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. 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 may be a material having good quantum efficiency for fluorescence or phosphorescence.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.

When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.

Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.

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.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

Comparative example

Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method.

First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the organic substrate to form a thickness of 10 nm. Subsequently, the inventive compound and the comparative example were vacuum deposited with a hole transport layer to a thickness of 20 nm. Vacuum deposition was carried out for comparative experiments. Subsequently, BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant, and the host material was 9,10-di- (naphthalene-2-anthracene) (hereinafter abbreviated as ADN), and the doping concentration was fixed at 4%. A comparative experiment was conducted. Subsequently, tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, which is an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic light emitting device by using Al / LiF as a cathode.

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was 1000 cd / m ^2. The T95 lifetime was measured using a life measurement instrument manufactured by McScience Inc. at the reference luminance.

Comparative Experimental Example

In order to compare the synthesized compound, an organic electroluminescent device having the same structure was manufactured using a compound represented by the following formula instead of the compound of the present invention as a hole transport layer material.

Material of hole transport layer Voltage
(V) Luminous efficiency
(cd / A) Luminous color Life (h) Comparative Example 1 NPD 5.72 6.15 blue 120.22 Example 1 Compound 1 5.49 6.34 blue 255.91 Example 2 Compound 2 4.99 6.21 blue 255.83 Example 3 Compound 3 4.95 6.17 blue 255.23 Example 4 Compound 61 4.81 6.37 blue 269.41 Example 5 Compound 62 4.83 6.21 blue 228.98 Example 6 Compound 63 4.99 6.56 blue 254.55 Example 7 Compound 88 4.88 6.12 blue 246.05 Example 8 Compound 89 4.65 6.96 blue 245.95 Example 9 Compound 90 4.71 6.70 blue 253.23 Example 10 Compound 121 4.90 6.14 blue 248.19 Example 11 Compound 122 4.53 6.88 blue 259.12 Example 12 Compound 123 4.87 6.54 blue 251.35 Example 13 Compound 163 5.03 6.54 blue 236.41 Example 14 Compound 164 5.52 6.24 blue 238.35 Example 15 Compound 165 5.50 6.09 blue 259.38 Example 16 Compound 175 5.54 6.00 blue 234.25 Example 17 Compound 176 5.44 6.57 blue 258.07 Example 18 Compound 177 5.18 6.34 blue 272.02

As can be seen from the results of the above table, the organic light emitting device using the organic light emitting device material of the present invention can not only improve color purity but also improve driving voltage significantly.

Therefore, the organic light emitting diode efficiency and lifespan characteristics can be remarkably improved based on these characteristics.

When the compounds not shown in Table 1 are used as the hole transport layer, the driving voltage, luminous efficiency, emission color, and lifespan are not only higher than those of the comparative example, but also higher in color purity and improved in driving voltage. We confirmed that there was. These results are substantially the same as Table 1 and omitted, but may form part of the present specification as necessary.

Although the luminous efficiency and driving characteristics of the compounds of the present invention were remarkably excellent through the tables of Examples and Comparative Examples, the substituents in the compounds of the Examples and Comparative Examples may be substituted with other substituents. Therefore, Examples and Comparative Examples in which the substituents in the compounds of the Tables of the Examples and Comparative Examples are substituted with other substituents may form part of the present specification.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (11)

A compound represented by one of the following formulae:
[Formula 1]

(2)

here,
R ₁ is a C ₁ to C ₆ alkyl group,
R ₂ and R ₃ are each independently hydrogen or a C ₆ to C ₂₀ aryl group; Or a C ₆ to C ₂₀ aryl group bonded to each other to form a ring,
R ₄ is a C ₁ ~ C ₆ alkyl group,
n and m are each independently an integer from 0 to 4,
l is an integer of 0 or 1,
o is an integer of 1 or 2,
L is a single bond, a C ₆ to C ₂₀ aryl group, or a divalent C ₆ to C ₂₀ aryl group,
Ar ₁ is a C ₆ ~ C ₂₀ aryl group,
Ar ₂ is a C ₆ ~ C ₂₀ aryl group; A fluorenyl group unsubstituted or substituted with a C ₁ to C ₆ alkyl group or a C ₆ to C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group and a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group containing one or more heteroatoms N or S. The method of claim 1,
Compounds, characterized in that the compound represented by one of the following formula.
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

delete The method of claim 2,
The compound is characterized in that one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound according to any one of claims 1, 2, and 4 as a hole transport layer material. The method of claim 5,
An organic electronic device, characterized in that to form an organic material layer by the solution process (soluble process). The method of claim 5,
The organic electroluminescent device is an organic electroluminescent device comprising an organic electroluminescent device comprising a first electrode, one or more organic material layers and a second electrode sequentially stacked. The method of claim 7, wherein
The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. delete A display device comprising the organic electroluminescent element of claim 5;
And a controller for driving the display device. The method of claim 10,
The organic electronic device is one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic TFT).

Images