KR20110076271A - Fluoranthene derivatives and organic electroluminescent device using the same - Google Patents

Abstract

PURPOSE: A fluoranthene derivative is provided to manufacture an organic electroluminescence device with excellent brightness, good luminous efficiency, lifetime property, and driving durability. CONSTITUTION: A fluoranthene derivative is represented by chemical formula 1. In chemical formula 1, R1-R10 are hydrogen, halogen, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C1-30 alkoxy group, substituted or unsubstituted C6-30 aryl group, substituted or unsubstituted C6-30 heteroaryl group, substituted or unsubstituted C5-30 cycloalkyl group, substituted or unsubstituted C5-30 heterocycloalkyl group, -N(Y1)(Y2), -Si(Y3)(Y4)(Y5), -S(Y6) or -O(Y7), wherein Y1-Y7 are hydrogen, substituted or unsubstituted C6-30 aryl group, substituted or unsubstituted C5-30 cycloalkyl group or substituted or unsubstituted C5-30 heterocycloalkyl group.

Description

Fluoranthene derivatives and organic electroluminescent devices using the same {Fluoranthene derivatives and organic electroluminescent device using the same}

The present invention relates to a fluoranthene derivative and an organic light emitting device using the same, and more particularly, to a fluoranthene derivative used as a light emitting material, and an organic light emitting diode having high luminescence brightness and luminous efficiency and improved lifetime characteristics. It is about.

An organic light emitting display device is an optical device that is applied to a flat panel display as a self-light emitting device using a principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. In addition, the organic light emitting device is a thin and lightweight light emitting device that provides high brightness at a low applied voltage and has a variety of emission wavelengths and high-speed response, particularly a two-layer organic light emitting device in which a hole transport layer and an electron transport layer are stacked. Since the report (CW Tang and SA Vanslyke, Applied Physics Letters Vol. 51, 913 (1987)) has attracted much attention as a large area light emitting device emitting light at low voltage. The stacked organic light emitting device has an anode (anode) / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (cathode) as a basic structure, the hole transport layer or electron transport layer of the structure layer of the light emitting layer It can also function. However, conventional organic light emitting diodes additionally require light output with high brightness or high conversion efficiency, and still have many problems in durability such as aging due to prolonged use and deterioration due to gas or moisture containing oxygen. It implies Recently, it is expected to apply the organic light emitting display device to a full color display, but the implementation of such a full color display requires three primary colors of blue, green, and red, and at present, a fluorescent material having a satisfactory efficiency cannot be presented. .

For example, although many aromatic compounds and condensed cyclic aromatic compounds have been studied as fluorescent organic compounds used in hole transport layers, light emitting layers and the like, it is difficult to say that compounds capable of sufficiently satisfying luminescence brightness and durability are obtained.

Therefore, many materials such as fluoranthene having high quantum efficiency have been studied as a material of an organic light emitting device.

The present invention is to solve the problems of the prior art as described above, and an object of the present invention is to provide an organic electroluminescent device having a high luminous brightness and luminous efficiency and a long driving time, and a fluoranthene derivative for realizing the same.

The present invention has been made in order to achieve the above object, by using a fluoranthene derivative represented by the following formula (1) as a light emitting material, high luminescence brightness and luminous efficiency, excellent life characteristics of the material, very drive life of the device It was found that an excellent organic electroluminescent device was obtained, and the present invention was completed.

Specifically, the present invention provides a fluoranthene derivative represented by the following Chemical Formula 1.

[Formula 1]

[In Formula 1,

R ₁ to R ₁₀ are each independently hydrogen, a halogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl Group, a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group, -N (Y ₁ ) ( Y ₂ ), —Si (Y ₃ ) (Y ₄ ) (Y ₅ ), —S (Y ₆ ) or —O (Y ₇ ), wherein Y ₁ to Y ₇ are independently hydrogen, substituted or unsubstituted A C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group; Wherein said heteroaryl group and heterocycloalkyl group comprise at least one hetero atom selected from B, N, O, S, P (= 0), Si and P.]

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

At this time, if there is no other definition in the technical terms used in the present invention, it has a meaning commonly understood by those skilled in the art to which the present invention belongs, and in the following description unnecessarily obscure the subject matter of the present invention. Description of known functions and configurations that may be omitted.

Substituents comprising 'alkyl' or 'alkoxy' as described herein include both straight chain or pulverized forms, and substituents comprising 'cycloalkyl' are not only monocyclic but also adamantyl or C ₇ -C ₃₀ bicyclo It also includes several ring-based hydrocarbons such as alkyl.

'Aryl' as described herein is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, preferably comprising a single or fused ring system comprising 4 to 7 members, more preferably 5 to 6 members, It also includes structures in which one or more aryls are bonded via chemical bonds.

In addition, in the description of "substituted or unsubstituted" in the description of "substituted" means a case that is further substituted with an unsubstituted substituent, the substituents further substituted with R ₁ to R ₁₀ are independently from each other -F, -Cl, -Br, -CN, -NO ₂ or -OH.

Further, the 'C ₁ -C ₃₀ alkyl group' described in the present invention includes a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₁₀ alkyl group, and the 'C ₁ -C ₃₀ alkoxy group' is a C ₁ -C ₂₀ alkoxy group or C _{A 1} -C ₁₀ alkoxy group, and the 'C ₆ -C ₃₀ aryl group' includes a C ₆ -C ₂₀ aryl group or a C ₆ -C ₁₀ aryl group. 'C ₆ -C ₃₀ heteroaryl group' comprises a C ₆ -C ₂₀ heteroaryl group or C ₆ -C ₁₀ heteroaryl group, and 'C ₅ -C ₃₀ cycloalkyl group' is a C ₅ -C ₂₀ cycloalkyl group or C ₅ -C ₁₀ cycloalkyl group.

R ₁ to R ₁₀ are independently selected from the following structures, but are not limited thereto.

[Wherein R ₁₁ to R ₂₃ are each independently hydrogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl Group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group.]

More specifically, R ₁ to R ₁₀ are each independently hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, decyl group, dodecyl group, hexadecyl group, fluorine group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentoxy group, i-pentoxy group, n-hexyloxy group, n-heptoxy group, cyclopropyl group, cyclobutyl group, Cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group , phenyl group , biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, azure Neyl group, heptarenyl group, acena ptylenyl group, phenenyl group, fluorenyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, ethyl- Risenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, hepta Phenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, thiophenyl group, indolyl group, furanyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, Pyrrolyl, pyrazolyl, imidazolyl, imidazolinyl, oxazolyl, thiazolyl, triazolyl, tetrazolyl, oxadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl , Pyrazinyl group, thianthrenyl group, cyclopentyl group, cyclohexyl group, oxiranyl group, pyrrolidinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, dimethylamino group, diethylamino group , Dipropylamino group, diisopropyl Mino group, dibutylamino group, di (sec-butyl) amino group, di (tert-butyl) amino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, methylpentylamino group, methylethylamino group, diphenylamino group , Di (4-trimethylsilylphenyl) amino group, di (2-methylphenyl) amino group, di (3-methylphenyl) amino group, di (4-methylphenyl) amino group, phenylnaphthylamino group, phenyl-4-trimethylphenylamino group, di ( 3,5-dimethylphenyl) amino group, di (3,4-dimethylphenyl) amino group, di (3,4,5-trimethylphenyl) amino group, dynaphthylamino group, trimethylsilyl group, triethylsilyl group, tripropylsilyl Group, triisopropylsilyl group, tributylsilyl group, tri (sec-butylsilyl group), tri (tert-butylsilyl group), tripentylsilyl group, trihexylsilyl group, triheptyl silyl group, trioctyl silyl group , Dimethylpentylsilyl group, triphenylsil It is selected from the group consisting of a aryl group, a trinaphthyl silyl group, a tri (2-methylphenyl) silyl group, a tri (3-methylphenyl) silyl group, a tri (4-methylphenyl) silyl group, or derivatives thereof. Do not.

The fluoranthene derivative according to the present invention is a blue light emitting material, and because of its characteristic three-dimensional structure, it is excellent in energy transfer, thereby showing high luminous efficiency. The fluoranthene derivative represented by Chemical Formula 1 may be more specifically exemplified as a compound represented by Chemical Formula 2 to Chemical Formula 33, but the following compound is not intended to limit the present invention.

 In another aspect, the present invention provides an organic light emitting display device, the organic light emitting display device according to the invention an anode; Cathode; And at least one organic compound layer interposed between the anode and the cathode, wherein the organic compound layer comprises at least one fluoranthene derivative of Formula 1.

The organic light emitting device including the fluoranthene derivative may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer between the anode and the cathode. The layer, the hole transport layer, the electron transport layer, and the electron injection layer serve to increase the probability of light emitting coupling in the light emitting layer by efficiently transferring holes or electrons to the light emitting layer. The hole injection layer and the hole transport layer are stacked to facilitate the injection of holes from the anode and the transport of the injected holes. In addition, a hole injection layer (HIL) may be further stacked below the hole transport layer, and the hole injection layer material may be used without particular limitation as long as it is commonly used in the art.

In addition, the organic compound layer further includes a light emitting layer, and the light emitting layer is stacked on top of the hole transport layer. The light emitting layer may be made of a single material, or may be made of a host / dopant, and a host and a dopant applied to the organic light emitting device of the present invention are particularly used as long as they are commonly used in the art. Can be used without limitation.

The fluoranthene derivative according to the present invention can be suitably used as a host material or a dopant material in forming the light emitting layer of the hole transport layer material, the organic light emitting device.

Hereinafter, a method of manufacturing an organic light emitting display device according to an embodiment of the present invention will be described with reference to FIG. 1. First, an anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used, and a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable.

In addition, as the anode material, materials commonly used in the art, such as transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), or zinc oxide (ZnO), may be used. have. A hole injection layer is selectively laminated on the anode by vacuum thermal deposition or spin coating, and then a hole transport layer is formed on the hole injection layer by vacuum thermal deposition or spin coating. The flowanthene derivative according to the present invention can be used in the hole transport layer. Next, after the light emitting layer is laminated on the hole transport layer, a hole blocking layer is selectively formed thereon by vacuum thermal evaporation or spin coating, and finally, the electron transport layer is vacuum-deposited or deposited on the hole blocking layer. After depositing through a spin coating method, the electron injection layer may be selectively formed, and the organic electroluminescent device according to the present invention may be manufactured by vacuum thermal deposition of a metal for forming a cathode on the electron injection layer. On the other hand, as the cathode forming metal, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) etc. can be used.

The fluoranthene derivatives according to the invention can also be used in electronic materials.

The organic electroluminescent device including the fluoranthene derivative prepared according to the present invention has not only excellent brightness, but also good luminous efficiency and excellent lifespan characteristics of the material.

Hereinafter, the present invention can be better understood by the following examples, which are intended to illustrate the present invention and are not intended to limit the protection scope of the present invention.

Preparation Example 1 Preparation of Compound 4

compound  1-1 Manufacture

1000 mL of ethanol and 180 g of sulfuric acid were added to a 2000 mL-3 neck round bottom flask, and 200 g (0.94 mol) of 4-bromophenylacetic acid was slowly added thereto, followed by stirring under reflux for 4 hours. At the end of the reaction, the temperature was reduced and extracted with 1500 mL of ether. After extraction, washed several times with distilled water and sodium bicarbonate solution, water was removed using anhydrous sodium sulfate, distillation under reduced pressure to obtain 180 g of compound 1-1 (yield 80%).

¹ H NMR (DMSO) δ 7.41 (d, 2H): 7.13 (d, 2H), 4.13 (q, 2H), 3.53 (t, 2H), 1.22 (t, 3H).

The synthetic route of compound 1-1 is shown in Scheme 1 below.

Scheme 1

compound 1-2 Manufacture

150 mL THF and 1000 mL of isopropylmagnesium were added to a 2000 mL-3 neck round bottom flask at a temperature of 0 ° C. or lower, and slowly added Compound 1-1 200 g (0.94 mol) was stirred for 1 hour. Stir for 15 hours. To this was added 300 mL of 10% ammonium chloride solution and 200 mL of 10% hydrochloric acid solution. The separated organic layer was washed with 200 mL of 10% NaOH aqueous solution, concentrated by distillation under reduced pressure. The concentrated liquid compound was put back into a 2000 mL-3 neck round bottom flask, and 1000 mL of acetic acid and 200 mL of 18% hydrochloric acid were added thereto, followed by stirring under reflux for 6 hours. When the reaction was terminated, the mixture was reduced in temperature, extracted with 200 mL ether, and distilled under reduced pressure to obtain 62 g of a compound 1-2 (yield 60%).

¹ H NMR (CDCl ₃ ) δ 7.44 (d, 4H): 7.00 (d, 4H), 3.67 (s, 5H)

The synthetic route of Compound 1-2 is shown in Scheme 2 below.

Scheme 2

compound 1-3 Manufacture

Into a 1000 mL-3 neck round bottom flask were placed 62 g (0.168 mol) of Compound 1-2 , 30.6 g (0.168 mol) of acenaphsenequinone from Sigma Aldrich, and 300 mL of ethanol under a nitrogen atmosphere, followed by stirring for 10 minutes. 4.70 g (0.084 mol) of KOH dissolved in 40 mL was added dropwise for 20 minutes, then stirred at room temperature for 30 minutes and filtered. The filtrate was washed several times with distilled water and dried to obtain 50 g of compound 1-3 (yield 58%).

¹ H NMR (DMSO) δ 8.08 (d, 2H): 7.79 (d, 2H), 7.73 (t, 2H), 7.59 (d, 4H), 7.43 (d, 4H).

The synthetic route of compound 1-3 is shown in Scheme 3 below.

Scheme 3

compound  1-4 Manufacture

10 mL (0.0195 mol) of Compound 1-3 , 3.74 g (0.021 mol) of diphenylacetylene from Sigma Aldrich, and 30 mL of diphenyl ester were added to a 250 mL-3 neck round bottom flask under nitrogen atmosphere. It was stirred at reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, and the crude compound was filtered and washed with methanol to give 10.7 g (yield 83%) of Compound 1-4 .

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.72 (d, 4H), 7.14-7.34 (m, 14H), 7.04 (d, 2H), 6.75 (d, 2H)

The synthetic route of Compound 1-4 is shown in Scheme 4 below.

Scheme 4

compound  4 Manufacture

After drying the 250 mL-3 neck round bottom flask completely, 25 g (0.036 mol) of Compound 1-4 were added under nitrogen atmosphere and dissolved with 75 mL of o-xylene. To this solution was added 17.4 g (0.079 mol) of 1-PNA, 293 mg of P (t-Bu) ₃ , 163 mg of Pd (OAc) ₂ and 8.33 g (0.086 mol) of Na ^t BuO, and the mixture was added for 3 hours. It was stirred at reflux. After cooling to room temperature, 75 mL of THF was added to increase fluidity and then added to 1500 mL of methanol. The resulting solid was filtered and washed with methanol to give 44.6 g (95% yield) of compound 4 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.92 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 7.13 (t, 4H ), 7.06 (d, 2H), 6.80-6.89 (m, 22H), 6.69 (d, 4H), 6.61 (d, 4H)

MALDI-TOF MS: m / z 941.11, cal. 941.16

The synthetic route of Compound 4 is shown in Scheme 5 below.

Scheme 5

Preparation Example 2 Preparation of Compound 7

compound  7 Manufacture

After 250 mL-necked round bottom flask was completely dried, 25 g (0.036 mol) of compounds 1-4 were added under nitrogen atmosphere and dissolved in 75 mL of o-xylene. To this solution was added 17.4 g (0.079 mol) of 2-PNA, 293 mg of P (t-Bu) ₃ , 163 mg of Pd (OAc) ₂ and 8.33 g (0.086 mol) of Na ^t BuO, and the mixture was added for 3 hours. It was stirred at reflux. After cooling to room temperature, 75 mL of THF was added to increase fluidity and then added to 1500 mL of methanol. The resulting solid was filtered and washed with methanol to give 44.6 g (95% yield) of compound 7 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.92 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 7.13 (t, 4H ), 7.06 (d, 2H), 6.80-6.89 (m, 22H), 6.69 (d, 4H), 6.48 (d, 4H).

The synthetic route of compound 7 is shown in Scheme 6 below.

Scheme 6

Preparation Example 3 Preparation of Compound 3

compound  3-1 Manufacture

10 g (0.0195 mol) of Compound 1-3 , 3.74 g (0.021 mol) of 4,4-dibromodiphenylacetylene from Sigma Aldrich, and 30 mL of diphenyl ester were added to a 250 mL 3-neck round bottom flask. It was stirred at reflux for 2 hours at 240 ℃. After the reaction was completed, the reaction mixture was cooled to room temperature, and the crude compound was filtered and washed with methanol to give 10.7 g (yield 83%) of compound 3-1 .

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.72 (d, 3H), 7.24-7.34 (m, 10H), 7.14 (d, 4H), 6.71 (d, 4H), 6.58 (d, 3H).

The synthetic route of compound 3-1 is shown in Scheme 7 below.

Scheme 7

compound  3 Manufacture

After 250 mL-necked round bottom flask was completely dried, 25 g (0.036 mol) of Compound 1-5 was added under nitrogen atmosphere, and dissolved with 75 mL of o-xylene. To this solution was added 17.4 g (0.079 mol) of 1-PNA, 293 mg of P (t-Bu) ₃ , 163 mg of Pd (OAc) ₂ and 8.33 g (0.086 mol) of Na ^t BuO, and the mixture was added for 3 hours. It was stirred at reflux. After cooling to room temperature, 75 mL of THF was added to increase fluidity and then added to 1500 mL of methanol. The resulting solid was filtered and washed with methanol to give 44.6 g (95% yield) of compound 3 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.90 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 7.13 (t, 4H ), 7.06 (d, 2H), 6.81-6.87 (m, 16H), 6.69 (d, 4H), 6.63 (d, 4H), 6.48 (d, 4H).

MALDI-TOF MS: m / z 841.15, cal. 841.05

The synthetic route of Compound 3 is shown in Scheme 8 below.

Scheme 8

Preparation Example 4 Preparation of Compound 9

compound  9 Manufacture

After 250 mL-necked round bottom flask was completely dried, 25 g (0.036 mol) of Compound 1-5 was added under nitrogen atmosphere, and dissolved with 75 mL of o-xylene. To this solution was added 17.4 g (0.079 mol) of 1-PNA, 293 mg of P (t-Bu) ₃ , 163 mg of Pd (OAc) ₂ and 8.33 g (0.086 mol) of Na ^t BuO, and the mixture was added for 3 hours. It was stirred at reflux. After cooling to room temperature, 75 mL of THF was added to increase fluidity and then added to 1500 mL of methanol. The resulting solid was filtered and washed with methanol to give 44.6 g (95% yield) of compound 9 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.92 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 7.13 (t, 4H ), 6.80-6.89 (m, 18H), 6.69 (d, 4H), 6.63 (d, 4H), 6.48 (d, 4H).

The synthetic route of compound 9 is shown in Scheme 9 below.

Scheme 9

Preparation Example 5 Preparation of Compound 15

compound  15 Manufacture

After 250 mL-necked round bottom flask was completely dried, 5 g (0.007 mol) of Compound 1-5 was added under nitrogen atmosphere, and dissolved with THF (75 mL) / H ₂ 0 (25 mL). 2 g (0.016 mol) of phenylboronic acid, 190 mg of PPh ₃ , 84 mg of Pd (OAc) ₂ and 4.1 g (0.03 mol) of K ₂ CO ₃ were added to the solution, and the mixture was stirred under reflux for 3 hours. . After cooling to room temperature, the resulting solid was filtered, washed with methanol to give 3.4 g (yield 70%) of compound 15 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.92 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 7.13 (t, 4H ), 7.06 (d, 2H), 6.80-6.89 (m, 14H), 6.67 (d, 4H), 6.63 (d, 4H), 6.58 (d, 4H).

MALDI-TOF MS: m / z 691.01, cal. 690.91.

The synthetic route of Compound 15 is shown in Scheme 10 below.

Scheme 10

Preparation Example 6 Preparation of Compound 28

compound  28 Manufacture

After completely drying the 250 mL-3 neck round bottom flask, add 5 g (0.007 mol) of 7- (4-Bromo-phenyl) -8,9,10-triphenyl-fluoranthene under nitrogen atmosphere and THF (75 mL) / H ₂ 0 (25 mL). To this solution was added 1.3 g (0.0077 mol) of 2-naphthylbronic acid, 85 mg of PPh ₃ , 42 mg of Pd (OAc) ₂ and 2 g (0.015 mol) of K ₂ CO ₃ , The mixture was stirred at reflux for 3 hours. After cooling to room temperature, the resulting solid was filtered and washed with methanol to give 44.6 g (yield 95%) of compound 28 after drying.

¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 7.92 (d, 2H), 7.80 (d, 2H), 7.40-7.44 (m, 4H), 7.20 (t, 2H), 6.80-6.89 (m , 18H), 6.63 (d, 4H)

MALDI-TOF MS: m / z 632.59, cal. 632.79.

The synthetic route of Compound 28 is shown in Scheme 11 below.

Scheme 11

Hereinafter, an embodiment of fabricating an organic light emitting diode using the hole transport materials of the present invention prepared as described above. In addition, Table 1 shows the results of electroluminescent properties and basic properties of the organic light emitting diodes manufactured according to Examples and Comparative Examples.

Example 1 Compound 3 Fabrication of Organic Light Emitting Diode

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. 2-TNATA of Compound 34 was deposited to a thickness of 600 kPa to form a hole injection layer. Subsequently, the compound 3 according to the present invention was deposited to have a thickness of 300 GPa to form a hole transport layer. To the compound 37 as a host material, a compound 38 was brought deposited such that 300 Å thickness to 7% by weight by using a host material, the following compound Alq ₃ 36 [tris (8-hydroxyquinoline) aluminum (Ⅲ)] Was deposited to a thickness of 200 kW to form a light emitting layer. Finally, aluminum and lithium were simultaneously deposited to form a cathode having a thickness of 1000 mW. The light emission test was performed by applying a voltage of 0 to 15V to the organic light emitting diode manufactured as described above, and Table 1 shows the results of measurement of electroluminescence properties and basic properties.

[Compound 34]

[Compound 35]

[Compound 36]

[Compound 37]

[Compound 38]

[Compound 39]

Example 2 Compound 4 Manufacture of Organic Light Emitting Diode Using

An organic light emitting diode was manufactured under the same conditions as in Example 1, except that Compound 1 was used instead of Compound 3 as the hole transport layer material in Example 1, and the results of electroluminescence and measurement of the basic physical properties are shown in Table 1 below. .

Example 3 Compound 7 Fabrication of Organic Light Emitting Diode

An organic light emitting diode was manufactured under the same conditions as in Example 1, except that Compound 1 was used instead of Compound 3 as the hole transport layer material in Example 1, and the results of electroluminescent properties and basic physical properties are shown in Table 1 below. .

Example 4 Compound 9 Manufacture of Organic Light Emitting Diode Using

An organic light emitting diode was manufactured under the same conditions as in Example 1, except that Compound 9 was used instead of Compound 3 as the hole transport layer material in Example 1, and the results of electroluminescent and basic physical properties are shown in Table 1 below. .

Example 5 Compound 28 Fabrication of Organic Light Emitting Diode

An organic light emitting diode was manufactured under the same conditions as in Example 1, except that Compound 28 was used instead of Compound 37 as a host material in Example 1, and Table 2 shows the results of electroluminescent properties and basic physical properties.

Comparative Example 1 Compound 35 Manufacture of Organic Light Emitting Diode Using

An organic light emitting diode was manufactured under the same conditions as in Example 1, except that Compound 1 was used as a well-known NPB of Chemical Formula 35 instead of Compound 3 in Example 1, and the electroluminescent properties and foundations shown in Table 1 below. Physical property measurement results are shown.

Comparative Example 2 Compound 39 Manufacture of Organic Light Emitting Diode Using

An organic light emitting diode was manufactured under the same conditions as in Comparative Example 1, except that Compound 39 was used instead of Compound 37 as a host material in Comparative Example 1, and the measurement results of the electroluminescent properties and the basic physical properties are shown in Table 2 below.

TABLE 1

TABLE 2

As shown in Table 1 and Table 2, it was confirmed that the luminescent properties of the fluoranthene derivatives developed in the present invention showed superior properties compared to conventional materials. In addition, the organic electroluminescent device using the fluoranthene derivative according to the present invention as the hole transport layer or the host material was excellent in luminous efficiency and improved power consumption compared to Comparative Examples 1 and 2.

1 is a cross-sectional view showing a laminated structure of an organic light emitting display device according to an embodiment of the present invention.

Figure 2 shows the luminous efficiency-luminance graph of the organic light emitting display device for Comparative Example 1 and Examples 1 to 4 of the present invention.

3 shows electroluminescence spectra of organic light emitting diodes according to Comparative Example 1 and Examples 1 to 4 of the present invention.

Figure 4 shows the luminous efficiency-luminance graph of the organic light emitting display device for Comparative Example 2 and Example 5 of the present invention.

5 shows electroluminescence spectra of organic light emitting diodes according to Comparative Example 2 and Example 5 of the present invention.

Claims (7)

Fluoranthene derivatives represented by the following formula (1). [Formula 1]

[In Formula 1, R ₁ to R ₁₀ are each independently hydrogen, a halogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group , Substituted or unsubstituted C ₆ -C ₃₀ heteroaryl group, substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group, -N (Y ₁ ) (Y ₂ ), -Si (Y ₃ ) (Y ₄ ) (Y ₅ ), -S (Y ₆ ) or -O (Y ₇ ), wherein Y ₁ to Y ₇ are independently hydrogen, substituted or unsubstituted. A C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group; Wherein said heteroaryl group and heterocycloalkyl group comprise at least one hetero atom selected from B, N, O, S, P (= 0), Si and P.] The method of claim 1, Substituents further substituted with R ₁ to R ₁₀ are independently from each other -F, -Cl, -Br, -CN, -NO ₂ or -OH fluoranthene derivative, characterized in that. The method of claim 1, R ₁ to R ₁₀ are independently selected from each other in the following structure fluoranthene derivatives.

[Wherein R ₁₁ to R ₂₃ are each independently hydrogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl Group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group or a substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group.] The method of claim 1, The fluoranthene derivative is a fluoranthene derivative, characterized in that the structure selected from the compound represented by the formula (2) to formula (33).

Anode; Cathode; And at least one organic compound layer interposed between the anode and the cathode, wherein the organic compound layer comprises at least one fluoranthene derivative of any one selected from claims 1 to 4. Electroluminescent element. The method of claim 5, The organic compound layer is an organic electroluminescent device, characterized in that it comprises a light emitting layer. An electronic material comprising the fluoranthene derivative of any one of claims 1 to 4.

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