KR101794795B1 - Hole transporting material and Organic electroluminescent display device using the same - Google Patents

Abstract

Wherein R 1, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group of C 1 to C 20, a substituted or unsubstituted C 5 to C 30 An aryl group, a polycyclic aromatic or polycyclic heterocyclic group of C3 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a C3 to C30 A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. Each of R 2, R 3, R 7 and R 8 is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group having a carbon number of C 5 to C 30, a hetero-arylene group having a carbon number of 3 to 30, A substituted or unsubstituted arylalkylene group of up to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and R5, R6, R10 , And R11 may include at least one of a vinyl group, an acryloyl group, a methacyloyl group, cyclic ethers, and siloxanes, A hole transporting material for an organic electroluminescence device, and a hole transporting material for an organic electroluminescence device.

Description

TECHNICAL FIELD The present invention relates to a hole transport material and an organic electroluminescent device using the same,

The present invention relates to a hole transport material and an organic electroluminescent device using the same. More specifically, the present invention relates to a hole transport material in which the dissolution characteristics with respect to an organic solvent are changed according to a curing process, and an organic electroluminescent device comprising the same.

In recent years, the demand for a flat display device having a small space occupancy has been increased due to the enlargement of the display device. The technology of the organic electroluminescent device, which is also called an organic light emitting diode (OLED) And several prototypes have already been announced.

An organic electroluminescent device is a device that injects electric charge into a light emitting material layer formed between an electron injecting electrode (cathode) and a hole injecting electrode (anode) to form an electron and a hole. The device can be formed on a flexible transparent substrate such as a plastic substrate and can be driven at a lower voltage (10 V or less) than a plasma display panel or an inorganic electroluminescence (EL) It also has the advantage of low power consumption and excellent color. In addition, organic electroluminescence (EL) devices can display three colors of green, blue, and red, making them a next-generation rich color display device and attracting a lot of interest from many people.

In general, an organic electroluminescent device includes an anode, a hole injecting layer (HIL), a hole transporting layer (HTL), an emitting material layer (EML), an electron transporting layer (ETL) an electron transporting layer, an electron injecting layer (EIL), and a cathode. In the case of the light emitting layer, it is composed of a host and a dopant. The holes and electrons are injected from the respective electrodes and recombine in the light emitting material layer while moving, thereby forming an exciton. The exciton emits light as it falls from the excited state to the ground state.

An organic electroluminescent device has to be manufactured by a solution process. In the case of the deposition process, when the second organic film is deposited on the first organic film, lamination is possible without loss of the lower film, but in the solution process, the solvent used in forming the upper film causes the lower film to be damaged by the lower film.

For example, when the light emitting material layer is formed on the hole transporting layer, the organic solvent of the light emitting material layer may cause damage to the hole transporting layer, thereby deteriorating the properties of the organic electroluminescence device and lowering the process yield .

An object of the present invention is to provide a material for a hole transporting layer which is excellent in solubility in an organic solvent and is capable of a solution process and can prevent damage by an organic solvent in a subsequent process.

R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group of C 1 to C 20, C 5 C30 substituted or unsubstituted aryl group, C3 to C30 polycyclic aromatic or polycyclic heterocyclic group, C6 to C30 substituted or unsubstituted aralkyl group an arylalkyl group, a substituted or unsubstituted cycloalkyl group of C3 to C30, a substituted or unsubstituted alkoxy group of C1 to C20, a substituted or unsubstituted aryloxyl group of C6 to C20, R2, R3, R7 and R8 are each selected from the group consisting of C1 to C20 substituted or unsubstituted alkylene group, C5 to C30 substituted or unsubstituted arylene group, C3 to C30 A hetero-arylene group, a substituted or unsubstituted arylalkylene group of C6 to C30, a C3 to C30 L is selected from carbon (C), oxygen (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, , At least two of R5, R6, R10 and R11 are a vinyl group, an acryloyl group, a methacyloyl group, cyclic ethers, siloxanes, A hole transporting material for an organic electroluminescence device, and a hole transporting material for an organic electroluminescence device.

The C1 to C20 substituted or unsubstituted alkyl group group is preferably a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, an? -dithifluoromethylbenzyl group, a triphenylmethyl group, and an? -benzyloxybenzyl group.

The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A 4-ethylhexylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, a 3,5-dichlorophenyl group, . ≪ / RTI >

The C3 to C30 polycyclic aromatic or aliphatic ring group is preferably a naphthyl group, a 1-methylnaphthyl group, a 2-methylnaphthyl group, an acenaphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group, a phenanthrenyl group, .

The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, o-methylbenzyl group, A p-hydroxybenzyl group, an m-hydroxybenzyl group, an o-hydroxybenzyl group, a p-iodobenzyl group, a p-iodobenzyl group, Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitro Benzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy- And a propyl group.

The C3 to C30 substituted or unsubstituted cycloalkyl group group is characterized by containing a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group and an adamantyl group.

The substituted or unsubstituted C1-C20 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, And a hexyloxy group.

The C6 to C20 substituted or unsubstituted aryloxy group group is characterized by including a phenoxy group, a tolyloxy group, and a naphthyloxy group.

At least two of R5, R6, R10 and R11 include a substituent of at least one of a 4-vinylphenyl group and a 4- (4-vinylbenzyl) oxymethylphenyl group.

R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10 and R 11 are other than methyl, ethyl, n- A C1 to C6 alkyl group such as n-propyl, i-propyl, n-butyl, i-butyl and t- and a substituent of any one of alkyl, cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium.

In another aspect, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; A light emitting material layer disposed between the first and second electrodes; And a hole transport layer disposed between the first electrode and the light emitting material layer, wherein the hole transport layer is represented by the following formula: wherein R1, R4, R5, R6, R9, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group of C5 to C30, a polycyclic aromatic or polycyclic heterocyclic group of C3 to C30, A substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30, a substituted or unsubstituted alkoxy group of C1 to C20 ), A substituted or unsubstituted aryloxy group of C6 to C20, R2, R3, R7 and R8 each represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted C5 to C30 A substituted or unsubstituted arylene group, a C3-C30 hetero-arylene group, C6-C3 L is selected from carbon (C), oxygen (O), or sulfur (S), wherein R is selected from the group consisting of a substituted or unsubstituted arylalkylene group of up to 0 carbon atoms and a substituted or unsubstituted cycloalkylene group of C3 to C30; m is an integer of 0 or 1 and n is an integer of 1 to 3 and at least two of R5, R6, R10 and R11 are a vinyl group, an acryloyl group, methacyloyl wherein the hole transporting material comprises at least one of cyclic ethers, siloxanes, cyclic ethers, and siloxanes.

At least two of R5, R6, R10 and R11 include a substituent of at least one of a 4-vinylphenyl group and a 4- (4-vinylbenzyl) oxymethylphenyl group.

The hole transport layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.

A hole injection layer disposed between the first electrode and the hole transport layer; An electron transport layer positioned between the light emitting material layer and the second electrode; And an electron injection layer located between the electron transport layer and the second electrode.

Since the hole transport material of the present invention is excellent in solubility in an organic solvent, a hole transport layer can be formed by a solution process. Therefore, it is easy to manufacture a large-area organic electroluminescent device.

In addition, cross-linking occurs due to the curing process, so that solubility in an organic solvent is not obtained, and damage due to a subsequent process can be prevented.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

Hereinafter, the structure of the hole transport material according to the present invention and its synthesis example and the organic electroluminescent device using the same will be described.

The hole transport material according to an embodiment of the present invention has a structure in which a substance capable of cross-linking to a center portion of a carbazole derivative and having excellent hole transporting ability is linked by a linker, .

Formula 1

The hole transporting material according to an embodiment of the present invention is excellent in solubility in an organic solvent and is characterized by having resistance to an organic solvent due to cross-linking caused by a curing process. That is, it does not dissolve in the organic solvent after the curing process.

Wherein R 1, R 4, R 5, R 6, R 9, R 10 and R 11 are each independently a substituted or unsubstituted alkyl group of C 1 to C 20 or a substituted or unsubstituted aryl group of C 5 to C 30 a polycyclic aromatic group or polycyclic heterocyclic group of C3 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted C3 to C30 group, A cycloalkyl group, a substituted or unsubstituted alkoxy group of C 1 to C 20, a substituted or unsubstituted aryloxy group of C 6 to C 20, and R 2 and R 3 , R7 and R8 each represent a substituted or unsubstituted alkylene group of C1-C20, a substituted or unsubstituted arylene group of C5-C30, a hetero-arylene group of C3-C30, a substituted or unsubstituted C6- An unsubstituted arylalkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30 Is selected. In particular, at least two of R5, R6, R10 and R11 are selected from materials having cross-linking properties and L is selected from carbon (C), oxygen (O) or sulfur (S). M is an integer of 0 or 1, and n is an integer of 1 to 3.

For example, the substituted or unsubstituted alkyl group group of C1 to C20 may be a methyl group, an ethyl group, a propyl group, an icopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, An alkenyl group such as an octyl group, a decanyl group, an octadecanyl group, a stearyl group, a 2-phenylisopropyl group, a trichloromethyl group, a trifluoromethyl group, a benzyl group, Benzyl group,? -Dithifluoromethylbenzyl group, triphenylmethyl group,? -Benzyloxybenzyl group.

The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A biphenyl group, a 4-methylbiphenyl group, a 4-ethylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, .

The polycyclic aromatic or aliphatic ring group of C3 to C30 includes naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, acenaphthyl, anthracenyl, can do.

The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o- Benzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzene group, A 1-hydroxy-2-phenylisopropyl group, a 1-chloro-2-phenylisopropyl group, a 1-hydroxybenzyl group, Group.

The substituted or unsubstituted cycloalkyl group group of C3 to C30 may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group, and an adamantyl group.

The substituted or unsubstituted alkoxy group of C1 to C20 is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert- And may include a period of silk gardens.

The C6 to C20 substituted or unsubstituted aryloxy group group may include a phenoxy group, a tolyloxy group, and a naphthyloxy group.

At least two of R5, R6, R10 and R11 may be a vinyl group, an acryloyl group, a methacyloyl group, a cyclic ethers, a siloxanes, Lt; RTI ID = 0.0 > crosslinked < / RTI > For example, the substituent having the above-mentioned crosslinking property may be a vinylphenyl group (4-vinylphenyl), a vinylbenzyloxymetaphenyl group (4- (4-vinylbenzyl) oxymethylphenyl) represented by the following Chemical Formula 2-1 and Chemical Formula 2-2 .

(2) -One

(2) -2

The substituents other than the substituents having the crosslinking property among R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 include methyl, ethyl, C 1 -C 6 alkyl such as n-propyl, i-propyl, n-butyl, i-butyl and t- May be any one of alkyl and cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium.

As described above, the hole transport material according to the embodiment of the present invention has a structure in which a substance capable of crosslinking is connected to the center of the carbazole derivative by a linker and has excellent solubility in an organic solvent. Therefore, A transport layer can be formed.

Further, since the solubility in the organic solvent is lost by the occurrence of crosslinking after the curing process, the organic solvent in the subsequent step is not damaged.

The hole transport material of the present invention represented by Formula 1 may be one of a plurality of materials represented by Formula 3 below. For convenience of explanation, symbols A1 to A148 were assigned to the bottom of each material.

(3)

Hereinafter, a hole-transporting material represented by A-1 in Formula 3 will be described as an example of the hole transporting material for an organic electroluminescence device according to the present invention.

Synthetic example

1. Synthesis of 9-phenyl-9H-carbazole

9-phenyl-9H-carbazole is synthesized by the following reaction formula 1.

Scheme 1

Specifically, carbazole (25mmol), iodobenzene (30mmol), CuI (1.25mmol), trans-1,2-diaminocyclohexane (6.25mmol) and K3PO4 (100mmol) were added to a two- necked round-bottomed flask. Was dissolved in 1,4-dioxane (125 mL), and the mixture was stirred in a bath at 130 ° C for 24 hours. After completion of the reaction, 1,4-dioxane was removed, and the mixture was extracted with dichloromethane and water, followed by distillation under reduced pressure. After the silica gel column, the solvent was distilled off under reduced pressure, and recrystallized from dichloromethane and methanol to obtain solid 9-phenyl-9H-carbazole (5 g).

2. Synthesis of 3,6-dibromo-9-phenyl-9H-carbazole

3,6-dibromo-9-phenyl-9H-carbazole is synthesized by the following Reaction Formula 2.

Scheme 2

Specifically, 9-phenyl-9H-carbazole (20 mmol) was dissolved in acetic acid (125 mmol) in a two-necked round bottom flask and bromine (45 mmol) was injected into a reaction vessel containing 5 ml of acetic acid using a syringe do. After the reaction vessel is stirred at room temperature for 1 hour, the reaction is terminated. Neutralize with water and NaOH, filter and rinse with ethanol 2-3 times. Hexane and dichloromathane were used for silica gel column. After recrystallization with dichloromethane and methanol, 6 g of solid 3,6-dibromo-9-phenyl-9H-carbazole was obtained.

3. Synthesis of N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine

N 3, N 6 -di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine is synthesized by the following reaction formula 3.

Scheme 3

Specifically, 3-dibromo-9-phenyl-9H-carbazole (10 mmol), 1-naphthylamine (22 mmol), Tris (dibenzylideneacetone) dipalladium (0) Bis (diphenylphosphino) -1,1'-binaphthalene (0.6 mmol) and sodium tert-butoxide (28 mmol) were dissolved in 30 ml of toluene and the mixture was stirred at 100 ° C for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. The silica gel column was distilled under reduced pressure to obtain 5.5 g of solid N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine.

4. Synthesis of (4-bromobenzyloxy) (tert-butyl) dimethylsilane

(4-bromobenzyloxy) (tert-butyl) dimethylsilane is synthesized by the following reaction formula (4).

Scheme 4

Specifically, 4-bromobenzylalcohol (30 mmol) and tert-butylchlorodimethylsilane (36 mmol) were dissolved in N, N-dimethylformamide (DMF) (50 ml), and imidazole (45 mmol) Dissolve in DMF and put into reaction vessel. The reaction vessel is adjusted to room temperature, stirred for 24 hours, and then the reaction is terminated. After extraction with hexane and water, the mixture was distilled under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure to obtain 8.6 g of 4-bromobenzyloxy (tert-butyl) dimethylsilane.

5. Synthesis of (N - (4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl)

(N - (4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl) -amine is synthesized by the following reaction formula 5.

Scheme 5

Specifically, a 2-neck round bottom flask was charged with 4-bromobenzyloxy (tert-butyl) dimethylsilane (20 mmol), 1-naphthylamine (22 mmol), Tris (dibenzylideneacetone) dipalladium (0) 2'-Bis (diphenylphosphino) -1,1'-binaphthalene (0.3 mmol) and sodium tert-butoxide (14 mmol) were dissolved in 30 mL of toluene and stirred in a bath at 100 ° C. for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure to obtain 4.7 g of a liquid (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (N-1-naphthyl) -amine.

6. Synthesis of 4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl

4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl is synthesized by the following reaction scheme 6.

Scheme 6

Specifically, a 2-necked round bottom flask was charged with (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl- (N-1-naphthyl) -amine (10 mmol), 4,4'-dibromobiphenyl dibenzylideneacetone dipalladium (0) (0.15 mmol), tri-tert-butylphosphine (0.3 mol) and sodium tert-butoxide (14 mmol) were dissolved in 30 mL of toluene and the mixture was stirred at 100 ° C. for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled under reduced pressure to obtain 2.3 g of solid 4-bromo-4 '- (((4-tert-butyl) dimethylsilyloxymethyl) phenyl) - (1-naphthyl) amino) biphenyl.

7. A process for the preparation of 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 1 -naphthyl- ) phenyl))) amino) phenyl) phenylcarbazole-3,6-diamine

9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (4- (N- 1 -naphthyl- ))) amino) phenyl) phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (7).

Scheme 7

Specifically, in a two-neck round bottom flask, N3, N6-di (naphthalen-1-yl) -9-phenyl-9H-carbazole-3,6-diamine (5 mmol), 4-bromo- Tris (dibenzylideneacetone) dipalladium (0) (0.15 mmol), tri-tert-butylphosphine (0.3 mol) and sodium tert-butoxide (14 mmol) were dissolved in toluene (30 mL), and the mixture was stirred in a bath at 100 ° C for 24 hours. After completion of the reaction, the toluene was removed, and the residue was extracted with dichloromethane and water, followed by distillation under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure, then recrystallized with dichloromethane and methanol and filtered to obtain solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6- N-1-naphthyl- (N - ((4-tert-butyl) dimethylsilyloxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine.

N, N-di (4- (4- (N-1-naphthyl- (N- (4-hydroxymethyl) phenyl) amino) phenyl) phenylcarbazole-3,6-diamine

Phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 1-naphthyl- phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (8).

Scheme 8

Specifically, a 2-neck round bottom flask was charged with 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- Tetrabutylammonium fluoride (TBAF) (4.8 ml, 1 M solution) was dissolved in THF (20 ml), and the solution was stirred at room temperature And stirred for 24 hours. After completion of the reaction, the THF was removed, and the solvent was distilled off under a silica gel column using hexane and ethyl acetate. Recrystallization using dichloromethane and methanol and filtration gave a solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, N6-di (4- (4- (N- 4-hydroxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine.

N 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (4- (N- phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine

N-di (4- (4- (N-1-naphthyl- (N- (4-fluorophenyl) (4-vinylbenzyl) oxymethyl) phenyl)) amino) phenyl) phenylcarbazole-3,6-diamine is synthesized by the following reaction formula (9).

Scheme 9

Specifically, a 2-necked round bottom flask was charged with 9-phenyl-N 3, N 6 -di (naphthalen-1-yl) -N 3, N 6 -di (4- (1 mmol) and NaH (3 mmol) were dissolved in DMF (30 mL). The mixture was stirred at room temperature for 1 hour, cooled to 0 ° C., and then injected into a syringe 4-vinylbenzyl chloride (3 mmol) was added thereto. After stirring for 24 hours at 100 ° C, the reaction mixture was extracted with dichloromethane and water and distilled under reduced pressure. After silica gel column, the solvent was distilled off under reduced pressure, recrystallized with dichloromethane and methanol and filtered to obtain solid 9-phenyl-N3, N6-di (naphthalen-1-yl) -N3, -1-naphthyl- (N- (4- (4-vinylbenzyl) oxymethyl) phenyl) amino) phenyl) phenylcarbazole-3,6-diamine 0.9 g.

Hereinafter, examples 1 through 3 of the organic electroluminescent device using the hole transport material for an organic electroluminescent device according to the present invention will be described. The hole transport material of the present invention and the organic electroluminescent device To compare the performance.

Experimental Example 1

The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-1 is dissolved in xylene and spin-coated (300 Å). Dried on a hot plate at 100 ° C for 10 minutes, and then cross-linked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 ^-6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.

Exhibited a 9mA / in ^{cm 2 473cd / m 2 (5.3V} ) The CIE x = 0.137, y = 0.239 , it exhibited a T (50) = 762hr in 1000nit. Here, T (50) is a time at which the luminance becomes half.

Experimental Example 2

The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-49 is dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 ^-6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.

Exhibited a 9mA / in ^{cm 2 443cd / m 2 (5.4V} ) The CIE x = 0.145, y = 0.236 , it exhibited a T (50) = 721hr in 1000nit.

Experimental Example 3

The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After drying on a hot plate at 150 ° C for 10 minutes to remove the solvent, the hole transport material A-61 is dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 ^-6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.

Exhibited a 9mA / in ^{cm 2 561cd / m 2 (5.1V} ) The CIE x = 0.143, y = 0.225 , it exhibited a T (50) = 890hr in 1000nit.

Comparative Example

The ITO layer was patterned to have a light emitting area of 3 mm x 3 mm on the substrate and then cleaned. After the substrate is mounted on a spin coater, PEDOT: PSS represented by the following Formulas 4-1 and 4-2 is spin-coated (500 Å) on the ITO layer. After the solvent was removed by drying on a hot plate at 150 ° C for 10 minutes, the hole transport material 2-NPD represented by the following chemical formula 4-5 was dissolved in xylene and spin-coated (300 Å). After drying for 10 minutes on a hot plate at 100 ° C, it is crosslinked by heating at 200 ° C for 30 minutes. The host AND represented by the following Formula 4-3 and a dopant DPAVBi (4%) represented by the following Formula 4-4 were dissolved in xylene and spin-coated (300 Å) on a hot plate at 100 ° C. for 10 minutes, And a base pressure of 1 × 10 ^-6 torr. Then, Alq 3 (350 Å), LiF (5 Å) and Al (500 Å) were deposited in this order.

Exhibited a 9mA / in ^{cm 2 422cd / m 2 (5.5V} ) The CIE x = 0.137, y = 0.241 , it exhibited a T (50) = 640hr in 1000nit.

Formula 4 -One

Formula 4 -2

Formula 4 -3

Formula 4 -4

Formula 4 -5

The comparison results of the above-described Experimental Examples 1 to 3 and Comparative Examples are shown in the following table. The unit of voltage is V, the unit of current is mA, the unit of luminance is cd / m2, the unit of current efficiency is cd / A, the unit of power efficiency is lm / W, the unit of T (50) to be.

Voltage electric current Luminance Current efficiency Power efficiency CIE (X) CIE (Y) T (50) Experimental Example 1 5.3 0.9 473 4.73 2.80 0.137 0.239 762 Experimental Example 2 5.4 0.9 443 4.43 2.58 0.145 0.236 721 Experimental Example 3 5.1 0.9 561 5.61 3.46 0.143 0.225 890 Comparative Example 5.5 0.9 422 4.22 2.41 0.137 0.241 640

As can be seen from Table 1, the efficiency of Experiments 1 to 3 was improved by about 5 to 30% as compared with Comparative Example by introducing the carbazole core derivative. That is, the hole transporting property was improved. Also, the life span was improved by 15 ~ 40%. Accordingly, it is possible to provide an organic electroluminescent device capable of manufacturing a large-area device by a coating method using the hole transporting material of the present invention, and having excellent luminous efficiency and improved lifetime.

An embodiment of an organic electroluminescent device including the above hole transporting material is shown in FIG.

As shown, the organic electroluminescent device includes first and second substrates (not shown) facing each other, and an organic light emitting diode (E) formed between the first and second substrates (not shown) .

The organic light emitting diode E includes a first electrode 110 serving as an anode, a second electrode 130 serving as a cathode, and an organic emission layer 120 formed between the first and second electrodes 110 and 130. [ ).

The first electrode 110 is made of a relatively high work function material such as indium-tin-oxide (ITO), and the second electrode 130 is made of a material having a relatively low work function value, For example, aluminum (Al) or an aluminum alloy (AlNd). In addition, the organic light emitting layer 120 has red, green, and blue organic light emission patterns.

The organic light emitting layer 120 may include a hole injection layer (HTL) 121, a hole transporting layer (HIL) 121, and a hole transporting layer (HIL) 121 sequentially from the first electrode 110 in order to maximize luminous efficiency. An emission layer 122, an emitting material layer (EML) 123, an electron transporting layer 124, and an electron injection layer 125.

Here, the hole transporting layer 122 includes the hole transporting material represented by Formula 1. As described above, the hole transporting material is dissolved in an organic solvent such as xylene to form the hole transporting layer 122 by a spin coating method or the like. When cross-linking is caused by a heat or light curing process, And does not have dissolution characteristics. Accordingly, when the light emitting material layer 123 is formed by the spin coating method after the formation of the hole transporting layer 122, damage to the hole transporting layer 122 is prevented by the organic solvent. For example, the hole transport layer 122 may be formed by a spin-coating process, a nozzle-printing process, an inkjet-printing process, a slot-coating process, a dip-coating process, a roll-to-roll process, or the like.

The organic electroluminescent device having such a structure has advantages in manufacturing a large area organic electroluminescent device because the hole transporting material is coated to form the hole transporting layer 122. In addition, the light emitting efficiency is improved, low power driving is possible, and lifetime is improved.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It can be understood that

110: first electrode
120: organic light emitting layer
121: Hole injection layer
122: hole transport layer
123: luminescent material layer
124: electron transport layer
125: electron injection layer
130: second electrode

Claims (14)

Is represented by the following formula,
R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A polycyclic aromatic group or polycyclic heterocyclic group of C30 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 a cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, and R2, R3, R7, R8 Each independently represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted arylene group of C5 to C30, a hetero-arylene group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C30 An alkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30, L is selected from the group consisting of carbon (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and at least two of R5, R6, R10 and R11 are selected from the group consisting of vinyl wherein the organic electroluminescent material has cross-linking properties including at least one of acryloyl group, methacyloyl group, cyclic ethers, and siloxanes. Hole transport material for devices.

The method according to claim 1,
The C1 to C20 substituted or unsubstituted alkyl group group is preferably a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, an? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -Methylphenylbenzyl group, a? -dithifluoromethylbenzyl group, a triphenylmethyl group,? -benzyloxybenzyl group, and a hole transporting material for an organic electroluminescence device.
The method according to claim 1,
The substituted or unsubstituted aryl group group of C5 to C30 is preferably a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a pentadecylphenyl group, a 2-trimethylsilylphenyl group, A 4-ethylhexylbiphenyl group, a 4-cyclohexylbiphenyl group, a terphenyl group, a 3,5-dichlorophenyl group, a 3,5-dichlorophenyl group, Transporting material for an organic electroluminescence element.
The method according to claim 1,
The C3 to C30 polycyclic aromatic or aliphatic ring group is preferably a naphthyl group, a 1-methylnaphthyl group, a 2-methylnaphthyl group, an acenaphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group, a phenanthrenyl group, Transporting material for an organic electroluminescence element.
The method according to claim 1,
The substituted or unsubstituted aralkyl group from C6 to C30 is preferably a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2- Naphthyl isopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-naphthyl isopropyl group, Chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-methylbenzyl group, o-methylbenzyl group, A p-hydroxybenzyl group, an m-hydroxybenzyl group, an o-hydroxybenzyl group, a p-iodobenzyl group, a p-iodobenzyl group, Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitro Benzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy- Wherein the electron transporting material comprises a propyl group.
The method according to claim 1,
The substituted or unsubstituted cycloalkyl group of C3 to C30 includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group, and an adamantyl group. .
The method according to claim 1,
The substituted or unsubstituted C1-C20 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, A hole transporting material for an organic electroluminescence device, and a hexyloxy group.
The method according to claim 1,
Wherein the C6 to C20 substituted or unsubstituted aryloxy group group comprises a phenoxy group, a tolyloxy group, and a naphthyloxy group.
The method according to claim 1,
Wherein at least two of R5, R6, R10 and R11 include at least one substituent selected from the group consisting of 4-vinylphenyl and 4- (4-vinylbenzyl) oxymethylphenyl. Hole transport material for devices.
The method according to claim 1,
R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10 and R 11 are other than methyl, ethyl, n- A C1 to C6 alkyl group such as n-propyl, i-propyl, n-butyl, i-butyl and t- wherein the organic compound contains a substituent selected from the group consisting of alkyl and cyanyl, trimethylsilyl, fluorine, trifluoromethyl, and deuterium. Hole transport material.
A first electrode;
A second electrode facing the first electrode;
A light emitting material layer disposed between the first and second electrodes;
And a hole transport layer disposed between the first electrode and the light emitting material layer,
The hole transport layer is represented by the following formula,
R 1, R 2, R 3, R 4, R 5, R 6, R 9, R 10 and R 11 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A polycyclic aromatic group or polycyclic heterocyclic group of C30 to C30, a substituted or unsubstituted aralkyl group of C6 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30 a cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, and R2, R3, R7, R8 Each independently represent a substituted or unsubstituted alkylene group of C1 to C20, a substituted or unsubstituted arylene group of C5 to C30, a hetero-arylene group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C30 An alkylene group, a substituted or unsubstituted cycloalkylene group of C3 to C30, L is selected from the group consisting of carbon (O) or sulfur (S), m is an integer of 0 or 1, n is an integer of 1 to 3, and at least two of R5, R6, R10 and R11 are selected from the group consisting of vinyl a hole transporting material having at least one of acryloyl group, methacyloyl group, cyclic ethers and siloxanes and having crosslinking properties, Organic electroluminescent device.

12. The method of claim 11,
Wherein at least two of R5, R6, R10 and R11 include at least one substituent selected from the group consisting of 4-vinylphenyl and 4- (4-vinylbenzyl) oxymethylphenyl. device.
12. The method of claim 11,
Wherein the hole transport layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
12. The method of claim 11,
A hole injection layer disposed between the first electrode and the hole transport layer;
An electron transport layer positioned between the light emitting material layer and the second electrode;
And an electron injection layer disposed between the electron transport layer and the second electrode.

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