KR20120052063A - Hole transporting material and organic electroluminescent display device using the same - Google Patents

Abstract

PURPOSE: A host transport material is provided to have excellent solubility to organic solvent, thereby forming a hole transport layer, thereby easily manufacturing large size organic electroluminescent device. CONSTITUTION: A host transport material is in chemical formula 1. In chemical formula 1, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 is respectively selected from a group consisting of a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C5-30 aryl group, a substituted or unsubstituted C3-30 polycyclic aromatic group or polycyclic heterocyclic group, a substituted or unsubstituted C6-30 arylalkyl group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C1-20 alkoxy group, a substituted or unsubstituted C6-20 arloxy group, L is selected from oxygen or sulfur, m is 0 or 1, n is an integer from 1-3, and at least two of R5, R6, R7, R10, R11 and R12 comprise at least one of a vinyl group, acryloyl group, a methacyloyl group, cyclic ethers, siloxanes.

Description

Hole transporting material and organic electroluminescent display device using the same

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

Recently, as the size of the display device increases, the demand for a flat display device having less space is increasing. As one of the flat display devices, an organic light emitting diode (OLED) technology, also called an organic light emitting diode (OLED), has a high speed. It has been developed and several prototypes have already been announced.

The organic electroluminescent device is a device that emits light when electrons and holes are paired and then disappear when electrons are injected into the light emitting material layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode). Not only can the device be formed on a flexible transparent substrate such as plastic, but it can also be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic electroluminescent (EL) display. In addition, the power consumption is relatively low, there is an advantage that the color is excellent. In addition, the organic electroluminescent (EL) device can display three colors of green, blue, and red, and thus, has become a subject of much interest as a next-generation rich color display device.

In general, organic light emitting diodes include an anode, a hole injecting layer (HIL), a hole transporting layer (HTL), an emitting material layer (EML), and an electron transport layer (ETL). It has a stacked structure of an electron transporting layer (EIL), an electron injecting layer (EIL), and a cathode. The light emitting layer includes a host and a dopant. Holes and electrons are injected from each electrode and move to recombine in the light emitting material layer to form excitons. The excitons fall from the excited state to the ground state to emit light.

A large area of the organic light emitting display device is required. For this purpose, an organic light emitting display device must be manufactured by a solution process. In the deposition process, when the second organic film is deposited on the first organic film, the lamination can be performed without loss of the lower film. However, in the solution process, the solvent used to form the upper film erodes the lower film, causing damage to the lower film.

For example, in the case of forming the light emitting material layer on the hole transport layer, the organic solvent of the light emitting material layer causes damage to the hole transport layer, thereby causing problems of deterioration of characteristics and process yield of the organic light emitting device. .

The present invention is excellent in solubility in organic solvents to enable a solution process and to provide a material of a hole transport layer that can prevent damage by organic solvents in a later process.

In order to solve the above problems, the present invention is represented by the following formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 are each substituted or furnished to C1 ~ C20 A substituted alkyl group, a substituted or unsubstituted aryl group of C5 ~ C30, a polycyclic aromatic group or polycyclic heterocyclic group of C3 ~ C30, C6 ~ C30 Substituted or unsubstituted arylalkyl group, C3-C30 substituted or unsubstituted cycloalkyl group, C1-C20 substituted or unsubstituted alkoxy group, C6 Is selected from a substituted or unsubstituted aryloxy group of ˜C20, 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, and at least two of R5, R6, R7, R10, R11, and R12 are a vinyl group, an acrylloyl group, and methacrylolyl It provides a transport material for an organic light emitting device characterized in that it has a cross-linking property, including at least one of (methacyloyl group), cyclic ethers, siloxanes (siloxanes).

The substituted or unsubstituted alkyl group group of C1 to C20 may be methyl, ethyl, propyl, icepropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, Decanyl, octadecanyl, stearyl, 2-phenylisopropyl, trichloromethyl, trifluoromethyl, benzyl, α-phenoxybenzyl, α-dimethylbenzyl, α-methylphenylbenzyl, It is characterized by including an α-ditrifluoromethylbenzyl group, a triphenylmethyl group and an α-benzyloxybenzyl group.

The substituted or unsubstituted aryl group group of C5 ~ C30 may be a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, pentaduthiumphenyl group, 2-trimethylsilylphenyl group, 3-trimethylsilylphenyl group, 4- Trimethylsilylphenyl group, 3,5-difluorophenyl group, 4-ethylphenyl group, biphenyl group, 4-menylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group It is characterized by including.

The C3-C30 polycyclic aromatic or heterocyclic group is a naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, acenaphthyl group, anthracenyl group, pulloenyl group, phenanyl group, phenan renyl group, pyrenyl group It is characteristic to include.

The substituted or unsubstituted aralkyl group group of C6 to C30 may be a benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α -Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β -Naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p -Methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o -Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p- Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-knight Benzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, 1-chloro-2-phenyliso It is characterized by including a profile group.

The substituted or unsubstituted cycloalkyl group group of C3 ~ C30 is characterized by including a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornene group, adamantyl group.

Substituted or unsubstituted alkoxy group of C1 ~ C20 is methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- butoxy group, heptyloxy group, It is characterized by including a hexyloxy group.

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

At least two of the R5, R6, R7, R10, R11, R12 comprises a substituent of at least one of the vinyl phenyl group (4-vinylphenyl), vinyl benzyloxy meth phenyl group (4- (4-vinylbenzyl) oxymethylphenyl) to be.

Among the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12, except for at least two of the R5, R6, R7, R10, R11, and R12, methyl (ethyl) and ethyl such as ethyl, n-propyl, i-propyl, i-propyl, n-butyl, i-butyl and t-butyl Characterized by containing a substituent of any of the alkyl group (C1 ~ C6) and cyanyl, cyanyl, trimethylsilyl, fluorine, trifluoromethyl, deuterium of C1 ~ C6 to be.

In another aspect, the present invention comprises a first electrode; A second electrode facing the first electrode; A light emitting material layer positioned 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, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 each represent a substituted or unsubstituted alkyl group of C1 to C20, a substituted or unsubstituted aryl group of C5 to C30, a polycyclic aromatic or heterocyclic group of C3 to C30, respectively. (polycyclic aromatic group or polycyclic heterocyclic group), substituted or unsubstituted arylalkyl group (C6-C30), substituted or unsubstituted cycloalkyl group (C3-C30), substitution of C1-C20 Or an unsubstituted alkoxy group, a C6-C20 substituted or unsubstituted aryloxy group, 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, and at least two of R5, R6, R7, R10, R11, R12 are non- It is a major transport material having crosslinking properties including at least one of vinyl group, acrylloyl group, methacryloyl group, cyclic ethers and siloxanes. Provided is an organic electroluminescent device characterized by being made.

At least two of the R5, R6, R7, R10, R11, R12 comprises a substituent of at least one of the vinyl phenyl group (4-vinylphenyl), vinyl benzyloxy meth phenyl group (4- (4-vinylbenzyl) oxymethylphenyl) to be.

The major 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, a roll-to-roll process.

A hole injection layer disposed between the first electrode and the hole transport layer; An electron transport layer between the light emitting material layer and the second electrode; It characterized in that it comprises an electron injection layer located between the electron transport layer and the second electrode.

Since the hole transport material of the present invention has excellent solubility in organic solvents, the hole transport layer may be formed by a solution process. Therefore, it is easy to manufacture a large area organic light emitting display device.

In addition, cross-linking occurs by the curing process so that it does not have solubility in an organic solvent, thereby preventing damage by a later process.

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

Hereinafter, the structure of the hole transport material according to the present invention, a synthesis example thereof, and an organic light emitting display device using the same will be described.

The hole transport material according to the embodiment of the present invention has a structure in which cross-linking is possible at the center of a fluorine derivative and a material having excellent hole transport ability is connected by a linker. Is displayed.

Formula 1

The hole transport material according to the embodiment of the present invention is excellent in solubility in organic solvents, crosslinking occurs by a curing process, and is characterized by having resistance to organic solvents. That is, it does not melt | dissolve in an organic solvent after a hardening process.

In Formula 1, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 each represent a substituted or unsubstituted alkyl group of C1 to C20, C5 to C30. Substituted or unsubstituted aryl group, C3-C30 polycyclic aromatic group or polycyclic heterocyclic group, C6-C30 Substituted or unsubstituted arylalkyl group ), A substituted or unsubstituted cycloalkyl group of C3-C30, a substituted or unsubstituted alkoxy group of C1-C20, a substituted or unsubstituted aryloxy group of C6-C20 ( aryloxy group). In particular, at least two of R5, R6, R7, R10, R11, and R12 are selected from materials having crosslinking properties, and L is selected from carbon (C), oxygen (O) or sulfur (S). In addition, m is an integer of 0 or 1, n is an integer of 1-3.

For example, a substituted or unsubstituted alkyl group from C1 to C20 may be methyl, ethyl, propyl, icepropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Octyl group, decanyl group, octadecanyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α-dimethylbenzyl group, α-methylphenyl Benzyl groups, α-ditrifluoromethylbenzyl groups, triphenylmethyl groups, α-benzyloxybenzyl groups.

The substituted or unsubstituted aryl group group of C5 ~ C30 is phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, pentaduthiumphenyl group, 2-trimethylsilylphenyl group, 3-trimethylsilylphenyl group, 4-trimethyl Silylphenyl group, 3,5-difluorophenyl group, 4-ethylphenyl group, biphenyl group, 4-menylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group It may include.

C3-C30 polycyclic aromatic or heterocyclic groups include naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, acenaphthyl group, anthracenyl group, pulluorenyl group, phenanyl group, phenan renyl group, pyrenyl group can do.

Substituted or unsubstituted aralkyl group groups from C6 to C30 are benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α- Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β- Naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p- Methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o- Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-amino Benzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl and m-nitroben Group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl It may include a group.

The substituted or unsubstituted cycloalkyl group group of C 3 to C 30 may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornene group, and adamantyl group.

Substituted or unsubstituted alkoxy group of C1-C20 is methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, heptyloxy group, hex It may include a siloxy group.

Substituted or unsubstituted aryloxy group group of C6 ~ C20 may include a phenoxy group, tolyloxy group, naphthyloxy group.

In addition, at least two of R5, R6, R7, R10, R11, and R12 may be a vinyl group, an acrylloyl group, a methacryloyl group, a cyclic ethers, a siloxane substituents having crosslinking properties such as siloxanes. For example, the substituent having the crosslinking property may be a vinylphenyl group (4-vinylphenyl) or a vinylbenzyloxymethaphenyl group (4- (4-vinylbenzyl) oxymethylphenyl) yl represented by the following Chemical Formulas 2-1 and 2-2. Can be.

Formula 2 -One

Formula 2 -2

In addition, except for including substituents having a crosslinking property among R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12, the remaining substituents are methyl and ethyl. , C1 to C6 such as n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, etc. An alkyl group of the alkyl and cyanyl (cyanyl), trimethylsilyl (trimethylsilyl), fluorine (fluorine), trifluoromethyl (trifluoromethyl), may be any one of deuterium (deuterium).

As described above, the hole transport material according to the embodiment of the present invention has a structure in which a material capable of crosslinking at the center of the fluorene derivative is linked by a linker, and has a good solubility in organic solvents. The transport layer can be formed.

In addition, since the solubility in the organic solvent is lost by crosslinking after the curing process, the organic solvent in the later process is not damaged.

The hole transport material of the present invention represented by Chemical Formula 1 may be one of a plurality of materials represented by Chemical Formula 3 below. For convenience of explanation, the symbols A1 to A118 are given at the bottom of each material.

(3)

Hereinafter, a synthesis example will be described taking as an example a hole transport material represented by A-1 in Formula 3 among the hole transport materials for an organic light emitting device according to the present invention.

Synthetic example

1.Synthesis of 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -fluorene-2,7-diamine

9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -fluorene-2,7-diamine is synthesized according to Scheme 1 below.

Scheme 1

Specifically, 2,7-dibromo-9,9-dihexylfluorene (10mmol), 1-naphthylamine (22mmol), Tris (dibenzylideneacetone) dipalladium (0) (0.3) in a two-necked round-bottomed flask mmol), (±) -2,2'-Bis (diphenylphosphino) -1,1'-binaphthalene (0.6 mmol) and sodium tert-butoxide (28 mmol) in Toluene (30 mL), Stirred for time. After completion of the reaction, toluene was removed, extracted with dichloromethane and water, distilled under reduced pressure, and the solvent was distilled under reduced pressure after silica gel column to obtain liquid 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -fluorene-2 5.5g of 7-diamine was obtained.

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

(4-bromobenzyloxy) (tert-butyl) dimethylsilane is synthesized by the following reaction formula 2.

Scheme 2

Specifically, 4-bromobenzylalcohol (30 mmol) and tert-butylchlorodimethylsilane (36 mmol) were dissolved in N, N-dimethylformamide (DMF) (50 ml) in a two-necked round bottom flask, and imidazole (45 mmol) was used at 0 ° C. using a syringe. It is dissolved in DMF and put into the reaction vessel. After the reaction vessel is adjusted to room temperature, the reaction is terminated after stirring for 24 hours. Extraction using hexane and water and distillation under reduced pressure followed by silica gel column distillation under reduced pressure yielded 8.6 g of a clear liquid (4-bromobenzyloxy) (tert-butyl) dimethylsilane.

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

(N-((4-tert-butyl) dimethylsilyloxymethyl) phenyl)-(N-1-naphthyl) -amine is synthesized according to Scheme 3 below.

Scheme 3

Specifically, (4-bromobenzyloxy) (tert-butyl) dimethylsilane (20mmol), 1-naphthylamine (22mmol), Tris (dibenzylideneacetone) dipalladium (0) (0.15mmol), (±) -2, 2'-Bis (diphenylphosphino) -1,1'-binaphthalene (0.3 mmol) and sodium tert-butoxide (14 mmol) were dissolved in toluene (30 mL), and then stirred in a 100 ° C. bath for 24 hours. After completion of the reaction, the toluene was removed, extracted with dichloromethane and water, distilled under reduced pressure, and the solvent was distilled under reduced pressure after silica gel column to obtain liquid (N-((4-tert-butyl) dimethylsilyloxymethyl) phenyl)-(N-1- 4.7 g of naphthyl) -amine were obtained.

4. 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 according to Scheme 4 below.

Scheme 4

Specifically, (N-((4-tert-butyl) dimethylsilyloxymethyl) phenyl)-(N-1-naphthyl) -amine (10mmol), 4,4'-dibromobiphenyl (11mmol), 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), followed by stirring in a 100 ° C. bath for 24 hours. After completion of the reaction, toluene is removed and 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 2.3g of solid 4-bromo-4 '-((((4-tert-butyl) dimethylsilyloxymethyl) phenyl)-(1-naphthyl) amino) biphenyl.

5.9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N-(((4-tert-butyl Synthesis of) dimethylsilyloxymethyl) phenyl))) amino) phenyl) phenylfluorene-2,7-diamine

9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N-(((4-tert-butyl) dimethylsilyloxymethyl ) phenyl))) amino) phenyl) phenylfluorene-2,7-diamine is synthesized according to Scheme 5 below.

Scheme 5

Specifically, 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -fluorene-2,7-diamine (5mmol), 4-bromo-4 '-(((( 4-tert-butyl) dimethylsilyloxymethyl) phenyl)-(1-naphthyl) amino) biphenyl (11mmol), Tris (dibenzylideneacetone) dipalladium (0) (0.15mmol), tri-tert-butylphosphine (0.3mol) and Sodium tert-butoxide (14 mmol) was dissolved in Toluene (30 mL) and stirred in a 100 ° C. bath for 24 hours. After the reaction, toluene is removed and extracted with dichloromethane and water. After silica gel column, the solvent was distilled off under reduced pressure, recrystallized using dichloromethane and Methanol and filtered to give solid 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- 4.5 g of (4- (N-1-naphthyl- (N-(((4-tert-butyl) dimethylsilyloxymethyl) phenyl))) amino) phenyl) phenylfluorene-2,7-diamine was obtained.

6. 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- (4-hydroxymethyl) phenyl)) Synthesis of amino) phenyl) phenylfluorene-2,7-diamine

9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- (4-hydroxymethyl) phenyl)) amino) Phenyl) phenylfluorene-2,7-diamine is synthesized by Reaction 6 below.

Scheme 6

Specifically, 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- ( ((4-tert-butyl) dimethylsilyloxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine (2mmol), tetrabutylammonium fluoride (TBAF) (4.8ml, 1M solution) was dissolved in THF (20mL), Stirred at room temperature for 24 hours. After completion of the reaction, THF was removed and the solvent was distilled off under reduced pressure after silica gel column using Hexane and ethyl acetate. Filter by recrystallization using dichloromethane and Methanol solid 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N -(4-hydroxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine 2.4 g was obtained.

7.9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- (4- (4-vinylbenzyl) Synthesis of oxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine (A-1)

9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- ( 4- (4-vinylbenzyl) oxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine is synthesized by the following Reaction Formula 7.

Scheme 7

Specifically, in a two-necked round bottom flask, 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4- (N-1-naphthyl- (N- ( 4-hydroxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine (1mmol), NaH (3mmol) was dissolved in DMF (30mL), stirred at room temperature for 1 hour, lowered to 0 ℃ and syringe 4-Vinylbenzyl chloride (3mmol) was added thereto. After stirring for 24 hours in a 100 ℃ bath, the reaction was terminated and extracted with dichloromethane and water and distilled under reduced pressure. After silica gel column, the solvent was distilled under reduced pressure, recrystallized with dichloromethane and Methanol, and then filtered to give solid 9,9-dihexyl-N2, N7-di (naphthalen-1-yl) -N2, N7-di (4- (4 0.9 g of-(N-1-naphthyl- (N- (4- (4-vinylbenzyl) oxymethyl) phenyl)) amino) phenyl) phenylfluorene-2,7-diamine was obtained.

Hereinafter, the hole transporting material according to the present invention and the organic light emitting device using the same through Experimental Examples 1 to 3 to fabricate the organic light emitting device using the hole transporting material for the organic light emitting device according to the present invention. Compare the performance of.

Experimental Example 1

The light emitting area of the indium tin oxide (ITO) layer on the substrate was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate on a spin coater spin-coating (500 Å) PEDOT: PSS represented by the following formulas 4-1 and 4-2 on the ITO layer. After drying for 10 minutes on a hot plate at 150 ° C to remove the solvent, the hole transport material A-1 is dissolved in xylene and spin-coated (300Å). After drying for 10 minutes on a hot plate of 100 ℃, it is cross-linked by heating at 200 ℃ 30 minutes. After the host AND represented by the following formula (4-3) and the dopant DPAVBi (4%) represented by the following formula (4-4) spin-coating a solution of xylene (300 Pa) and dried for 10 minutes on a hot plate of 100 ℃, vacuum After mounting in the chamber and having a base pressure of 1 × 10 ⁻⁶ torr, the films were formed in the order of Alq 3 (350 Pa), LiF (5 Pa), and Al (500 Pa).

460 cd / m ² (5.4 V) at 10 mA / cm ² , and T (50) = 780 hr at CIE x = 0.135, y = 0.243, and 1000 nits. Here, T 50 is a time at which the luminance is half.

Experimental Example 2

The light emitting area of the indium tin oxide (ITO) layer on the substrate was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate on a spin coater spin-coating (500 Å) PEDOT: PSS represented by the following formulas 4-1 and 4-2 on the ITO layer. After drying for 10 minutes on a hot plate at 150 ℃ to remove the solvent, the hole transport material A-33 is dissolved in xylene spin-coating (300 (). After drying for 10 minutes on a hot plate of 100 ℃, cross-linked by heating at 200 ℃ 30 minutes. After the host AND represented by the following formula (4-3) and the dopant DPAVBi (4%) represented by the following formula (4-4) spin-coating a solution of xylene (300 Pa) and dried for 10 minutes on a hot plate of 100 ℃, vacuum After mounting in the chamber and having a base pressure of 1 × 10 ⁻⁶ torr, the films were formed in the order of Alq 3 (350 Pa), LiF (5 Pa), and Al (500 Pa).

438 cd / m ² (5.5 V) at 10 mA / cm ² , and T (50) = 730 hr at CIE x = 0.147, y = 0.239, and 1000 nits.

Experimental Example 3

The light emitting area of the indium tin oxide (ITO) layer on the substrate was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate on a spin coater spin-coating (500 Å) PEDOT: PSS represented by the following formulas 4-1 and 4-2 on the ITO layer. After drying for 10 minutes on a hot plate at 150 ° C to remove the solvent, spin-coating (30069) by dissolving the hole transport material A-69 in xylene (xylene). After drying for 10 minutes on a hot plate of 100 ℃, cross-linked by heating at 200 ℃ 30 minutes. The host AND represented by the following formula (4-3) and the dopant DPAVBi (4%) represented by the following formula (4-4) was spin-coated a solution of xylene (300 Pa) and dried for 10 minutes on a hot plate of 100 ℃, vacuum After mounting in the chamber and having a base pressure of 1 × 10 ⁻⁶ torr, the films were formed in the order of Alq 3 (350 Pa), LiF (5 Pa), and Al (500 Pa).

556 cd / m ² (5.2 V) at 10 mA / cm ² , and T (50) = 930 hr at CIE x = 0.142, y = 0.228, 1000 nits.

Comparative example

The light emitting area of the indium tin oxide (ITO) layer on the substrate was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate on a spin coater spin-coating (500 Å) PEDOT: PSS represented by the following formulas 4-1 and 4-2 on the ITO layer. After drying for 10 minutes on a hot plate at 150 ℃ to remove the solvent, the hole transport material 2-NPD represented by the following formula 4-5 is dissolved in xylene and spin-coating (300Å). After drying for 10 minutes on a hot plate of 100 ℃, cross-linked by heating at 200 ℃ 30 minutes. The host AND represented by the following formula (4-3) and the dopant DPAVBi (4%) represented by the following formula (4-4) was spin-coated a solution of xylene (300 Pa) and dried for 10 minutes on a hot plate of 100 ℃, vacuum After mounting to the chamber and having a base pressure of 1 × 10 ⁻⁶ torr, films were formed in the order of Alq 3 (350 Pa), LiF (5 Pa), and Al (500 Pa).

422 cd / m ² (5.5 V) at 10 mA / cm ² , with T (50) = 640 hr at CIE x = 0.137, y = 0.241, 1000 nits.

Formula 4 -One

Formula 4 -2

Formula 4 -3

Formula 4 -4

Formula 4 -5

Comparison results of the above Experimental Examples 1 to 3 and Comparative Example are shown in the table below. The unit of voltage is V, the unit of current is mA, the unit of brightness is cd / m2, the unit of current efficiency is cd / A, the unit of power efficiency is lm / W, and the unit of T (50) is time (hr). to be.

Voltage electric current Luminance Current efficiency Power efficiency CIE (X) CIE (Y) T (50) Experimental Example 1 5.4 0.9 460 4.60 2.68 0.135 0.243 780 Experimental Example 2 5.5 0.9 438 4.38 2.50 0.147 0.239 730 Experimental Example 3 5.2 0.9 556 5.56 3.36 0.142 0.228 930 Comparative example 5.5 0.9 422 4.22 2.41 0.137 0.241 640

As can be seen from Table 1, Experimental Example 1 to Experimental Example 3 was improved by about 10 to 15% compared to the comparative example by introducing a fluorene core derivative. In other words, the hole transport characteristics are improved. In addition, lifespan is improved by 15-50%. Therefore, it is possible to manufacture a large area device by the coating method using the hole transport material of the present invention, it is possible to provide an organic light emitting device having excellent luminous efficiency and improved lifetime.

An embodiment of an organic light emitting display device including the hole transport material is shown in FIG. 1.

As illustrated, the organic light emitting diode 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 is an organic light emitting layer 120 formed between the first electrode 110 serving as an anode, the second electrode 130 serving as a cathode, and the first and second electrodes 110 and 130. )

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

The organic light emitting layer 120 has a multi-layer structure, that is, a hole injection layer (HTL) 121, a hole transporting layer (HIL) in order to maximize the luminous efficiency sequentially from the first electrode 110 ) 122, an emitting material layer (EML) 123, an electron transporting layer 124, and an electron injection layer 125.

Here, the hole transport layer 122 comprises a hole transport material represented by the formula (1). As described above, the hole transport material is dissolved in an organic solvent such as xylene to form the hole transport layer 122 by spin coating or the like, and when crosslinking occurs by a curing process by heat or light, It does not have dissolution characteristics. Therefore, when the light emitting material layer 123 is formed by the spin coating method after the hole transport layer 122 is formed, damage to the hole transport layer 122 is prevented by an organic solvent. For example, the hole transport layer 122 may be a spin-coating process, a nozzle printing process, an inkjet printing process, a slot coating process, or a dip coating process. It may be formed by a dip-coating process, a roll-to-roll process and the like.

The organic light emitting diode having such a structure has an advantage in manufacturing a large area organic light emitting diode because it forms the hole transport layer 122 by coating a hole transport material. In addition, the luminous efficiency is improved to enable a low power drive has the advantage of improving the life.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the present invention described in the claims below I can understand that you can.

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

Claims (14)

It is represented by the following formula,
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 each represent a substituted or unsubstituted alkyl group up to C1 to C20, a substituted or unsubstituted C5 to C30 Aryl group, C3 ~ C30 polycyclic aromatic group or polycyclic heterocyclic group, C6 ~ C30 substituted or unsubstituted arylalkyl group, C3 ~ From a substituted or unsubstituted cycloalkyl group of C 30, a substituted or unsubstituted alkoxy group of C 1 to C 20, a substituted or unsubstituted aryloxy group of C 6 to C 20 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, and R5, R6, R7, R10, R11 At least two of R12 are at least one of a vinyl group, an acrylloyl group, a methacryloyl group, a cyclic ether, and a siloxanes. A major transport material for an organic light emitting device, characterized in that it has a cross-linking property, including one.

The method of claim 1,
The substituted or unsubstituted alkyl group group of C1 to C20 may be methyl, ethyl, propyl, icepropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, Decanyl, octadecanyl, stearyl, 2-phenylisopropyl, trichloromethyl, trifluoromethyl, benzyl, α-phenoxybenzyl, α-dimethylbenzyl, α-methylphenylbenzyl, A major transport material for an organic electroluminescent device, characterized by comprising an α-ditrifluoromethylbenzyl group, a triphenylmethyl group, and an α-benzyloxybenzyl group.
The method of claim 1,
The substituted or unsubstituted aryl group group of C5 ~ C30 may be a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, pentaduthiumphenyl group, 2-trimethylsilylphenyl group, 3-trimethylsilylphenyl group, 4- Trimethylsilylphenyl group, 3,5-difluorophenyl group, 4-ethylphenyl group, biphenyl group, 4-menylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group A major transport material for an organic light emitting device, characterized in that it comprises a.
The method of claim 1,
The C3-C30 polycyclic aromatic or heterocyclic group is a naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, acenaphthyl group, anthracenyl group, pulloenyl group, phenanyl group, phenan renyl group, pyrenyl group A major transport material for an organic light emitting device, characterized in that it comprises.
The method of claim 1,
The substituted or unsubstituted aralkyl group group of C6 to C30 may be a benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α -Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β -Naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p -Methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o -Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p- Aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-knight Benzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, 1-chloro-2-phenyliso A major transport material for an organic light emitting device, characterized in that it comprises a propyl group.
The method of claim 1,
The substituted or unsubstituted cycloalkyl group group of C3 ~ C30 is a transport material for an organic light emitting device, characterized in that it comprises a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornene group, adamantyl group .
The method of claim 1,
Substituted or unsubstituted alkoxy group of C1 ~ C20 is methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- butoxy group, heptyloxy group, A major transport material for an organic light emitting device, characterized in that it contains a hexyloxy group.
The method of claim 1,
The substituted or unsubstituted aryloxy group group of C6 ~ C20 is a major transport material for an organic light emitting device, characterized in that it includes a phenoxy group, tolyloxy group, naphthyloxy group.
The method of claim 1,
At least two of the R5, R6, R7, R10, R11, R12 comprises a substituent of at least one of the vinyl phenyl group (4-vinylphenyl), vinyl benzyloxy meth phenyl group (4- (4-vinylbenzyl) oxymethylphenyl) Major transport material for phosphorus organic electroluminescent device.
The method of claim 1,
Among the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12, except for at least two of the R5, R6, R7, R10, R11, and R12, methyl (ethyl) and ethyl such as ethyl, n-propyl, i-propyl, i-propyl, n-butyl, i-butyl and t-butyl Characterized by containing a substituent of any of the alkyl group (C1 ~ C6) and cyanyl, cyanyl, trimethylsilyl, fluorine, trifluoromethyl, deuterium of C1 ~ C6 Major transport material for phosphorus organic electroluminescent device.
A first electrode;
A second electrode facing the first electrode;
A light emitting material layer positioned between the first and second electrodes;
A hole transport layer disposed between the first electrode and the light emitting material layer;
The major transport layer is represented by the following formula,
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 each represent a substituted or unsubstituted alkyl group up to C1 to C20, a substituted or unsubstituted C5 to C30 Aryl group, C3 ~ C30 polycyclic aromatic group or polycyclic heterocyclic group, C6 ~ C30 substituted or unsubstituted arylalkyl group, C3 ~ From a substituted or unsubstituted cycloalkyl group of C 30, a substituted or unsubstituted alkoxy group of C 1 to C 20, a substituted or unsubstituted aryloxy group of C 6 to C 20 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, and R5, R6, R7, R10, R11 At least two of R12 are at least one of a vinyl group, an acrylloyl group, a methacryloyl group, a cyclic ether, and a siloxanes. Organic electroluminescent device, characterized in that made of a major transport material having a cross-linking property, including one.

The method of claim 11,
At least two of the R5, R6, R7, R10, R11, R12 comprises a substituent of at least one of the vinyl phenyl group (4-vinylphenyl), vinyl benzyloxy meth phenyl group (4- (4-vinylbenzyl) oxymethylphenyl) Phosphorescent organic light emitting device.
The method of claim 11,
The major transport layer is an organic light emitting display device, characterized in that 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, a roll-to-roll process.
The method of claim 11,
A hole injection layer disposed between the first electrode and the hole transport layer;
An electron transport layer between the light emitting material layer and the second electrode;
And an electron injection layer positioned between the electron transport layer and the second electrode.

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