CN1980884A - Aromatic amine derivative and organic electroluminescent device using the derivative - Google Patents

Abstract

The present invention discloses an aromatic amine derivative having a special structure of a  structure. Also disclosed is an organic electroluminescent device, wherein an organic thin film comprises one or more layers including at least one light emitting layer, the organic thin film layer is sandwiched between an anode and a cathode, and at least one layer of the organic thin film comprises the aromatic amine derivative itself or a mixture component thereof. Such an organic electroluminescent device has a long service life and high luminous efficiency, and emits blue light with high color purity. The aromatic amine derivative can realize such an organic electroluminescent device.

Description

Aromatic amine derivative and organic electroluminescent device using the derivative

technical field

[0001]

The present invention relates to an aromatic amine derivative and an organic electroluminescence device using the derivative, more particularly, to a device with long lifetime, high-efficiency luminescence and emission An organic electroluminescent device with high-purity blue light; and an aromatic amine derivative capable of realizing the organic electroluminescent device.

Background of the invention

[0002]

Organic electroluminescence (hereinafter, "electroluminescence" is sometimes referred to as "EL") device using an organic substance is currently expected to be used as an inexpensive full-color display of a solid-state light-emitting type with a large size. Regarding organic EL Various studies of the device are in progress. An organic EL device generally has a structure including a light-emitting layer and a pair of electrodes sandwiching the light-emitting layer. Light emission of an organic EL device is a phenomenon in which, when an electric field is applied between two poles, electrons are injected from the cathode side and electron holes are injected from the anode side, and the electrons combine with the holes in the emissive layer to form excitation state, the energy generated when the excited state returns to the ground state is emitted as light.

Conventional organic EL devices require a high driving voltage and exhibit only low luminance or inefficient light emission compared to inorganic light emitting diodes. In addition, the degradation characteristics of conventional organic EL devices are also very wasteful, and therefore, are not actually used. Although organic EL devices have been gradually developed in recent years, it is still required to develop an organic EL device having a high light emission efficiency and a long service life.

For example, a technique using a single monoanthracene compound as an organic light-emitting substance is now disclosed (refer to the following Patent Document 1). However, in this technology, the luminance obtained by using this substance is as low as 1650cd/m ² , for example, the current density is 165mA/cm ² , and its light emission efficiency is also very low, that is, only 1cd/A, which cannot be practically application. A technique using a single dianthracene compound as an organic light-emitting substance is also currently disclosed (refer to the following Patent Document 2). However, also in this technique, the luminous efficiency obtained with this substance is as low as about 1-3 cd/A. Therefore, there is a need for an improved technique to make it practically applicable. In addition, a technique of using a distyryl compound and adding styrylamine or the like as an organic light-emitting substance has also been disclosed (refer to the following Patent Document 3). However, the device disclosed therein does not exhibit a sufficiently long life and, therefore, further improvement is required.

In addition, there is now disclosed a technique of using a mono- or dianthracene compound and a distyryl compound as an organic light-emitting intermediate layer (refer to the following Patent Document 4). However, in these techniques, the conjugated structure of the styrene compound lengthens the wavelength of the emission spectrum and destroys the color purity.

(chrysene)衍生物的发射蓝光装置。但是，尽管在光发射效率上具有优越性，由于该装置寿命不足，还需进一步改善。In addition, the following Patent Document 5 discloses the use of diamino

(chrysene) derivative blue light emitting device. However, despite the superiority in light emission efficiency, further improvement is required due to the short lifetime of the device.

[0003]

Patent Document 1: Japanese Unexamined Patent Application

Special Opening No. Hei 11-3782A

Patent Document 2: Japanese Unexamined Patent Application

Special Opening No. Hei 8(1996)-012600

Patent Document 3: International Patent Application Publication PCT No. WO00/06402

Patent Document 4: Japanese Unexamined Patent Application

   Special Application No. 2001-284050

Patent Document 5: International Application Publication PCT No. WO04/04088

invention disclosure

[0004]

The present invention has overcome the above-mentioned problems. An object of the present invention is to provide an organic EL device having a long service life and high-efficiency light emission, and an arylamine derivative capable of realizing such an organic EL device.

[0005]

结构结合。在上述发现的基础上实现了本发明。As a result of extensive research on the development of arylamine derivatives having the above-mentioned suitable properties and organic EL devices using the arylamine derivatives, the present inventors have found that the object of the present invention can be obtained by using the following general formula (1) or (2) ) represented by arylamine derivatives, wherein the amino and substituted

Structure combined. The present invention has been accomplished on the basis of the above findings.

[0006]

That is, the present invention provides an arylamine derivative represented by the following general formula (1) or general formula (2):

[0007]

In the general formula (1), A ₁ to A ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted alkyl group having 5-50 ring carbon atoms Aryl, substituted or unsubstituted aralkyl having 1-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 3-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 1-50 carbon atoms Substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy with 5-50 ring carbon atoms, substituted or unsubstituted arylamino with 5-50 ring carbon atoms, 1- A substituted or unsubstituted alkylamino group with 20 carbon atoms, a substituted or unsubstituted heterocyclic group with 3-50 ring carbon atoms, a substituted or unsubstituted silane with 3-50 carbon atoms group or halogen atom.

a, b, c and d each independently represent an integer of 0-5, when a, b, c or d are each an integer of 2 or more, _A1 to _A4 can be the same or different from each other, and can be combined with each other to form A saturated or unsaturated ring; and in addition, a pair of A ₁ and A ₂ and a pair of A ₃ and A ₄ can be combined with each other to form a saturated or unsaturated ring;

R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms, a substituted or unsubstituted aryl group having 6-50 substituted or unsubstituted aralkyl with 3 ring carbon atoms, substituted or unsubstituted cycloalkyl with 3-50 ring carbon atoms, substituted or unsubstituted aryl with 5-20 ring carbon atoms Amino, substituted or unsubstituted alkylamino with 1-20 carbon atoms, substituted or unsubstituted heterocyclic group with 3-50 ring carbon atoms or substituted or unsubstituted with 3-50 carbon atoms Unsubstituted silyl groups; a pair of R ₁ and R ₂ and a pair of R ₃ and R ₄ can be combined with each other to form a saturated or unsaturated ring;

However, the case where all R ₁ to R ₄ are hydrogen atoms in the general formula (1) is excluded.

[0008]

In the general formula (2), A ₅ to A ₈ each independently represent a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms , a substituted or unsubstituted cycloalkyl group having 3-50 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 3-50 ring carbon atoms;

R ₅ to R ₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms, a substituted or unsubstituted aryl group having 6-50 substituted or unsubstituted aralkyl with 3 ring carbon atoms, substituted or unsubstituted cycloalkyl with 3-50 ring carbon atoms, substituted or unsubstituted aryl with 5-20 ring carbon atoms Amino, substituted or unsubstituted alkylamino with 1-20 carbon atoms or substituted or unsubstituted heterocyclic group with 3-50 ring carbon atoms; and a pair of R ₅ and R ₆ and a pair of R ₇ and R ₈ may combine with each other to form a saturated or unsaturated ring.

[0009]

In addition, the present invention provides an organic EL device comprising at least one organic thin film layer comprising a light emitting layer sandwiched between an electrode pair consisting of an anode and a cathode, wherein at least one organic thin film layer Contains a single said arylamine derivative or a mixture thereof.

[0010]

The organic EL device using the arylamine derivative of the present invention exhibits practically sufficient brightness even at a very low external discharge voltage, exhibits increased luminous efficiency, and exhibits resistance to deterioration after long-term use. properties, thus showing its extended service life.

Graphic brief description

[0011]

Fig. 1 is a diagram showing the relevant ¹ H-NMR measurement results of compound (4) obtained in Synthesis Example 1;

Figure 2 is a graph showing the ¹ H-NMR measurement results related to the compound (9) obtained in Synthesis Example 2;

Figure 3 is a graph showing the ¹ H-NMR measurement results related to the compound (20) obtained in Synthesis Example 3;

Fig. 4 is a graph showing the measurement results of ¹ H-NMR related to the compound (23) obtained in Synthesis Example 4;

Fig. 5 is a graph showing the measurement results of ¹ H-NMR related to the compound (25) obtained in Synthesis Example 5;

Fig. 6 is a graph showing the measurement results of ¹ H-NMR related to the compound (39) obtained in Synthesis Example 6;

Fig. 7 is a graph showing the measurement results of ¹ H-NMR related to the compound (57) obtained in Synthesis Example 7;

Fig. 8 is a graph showing the measurement results of ¹ H-NMR related to the compound (95) obtained in Synthesis Example 8;

Fig. 9 is a graph showing the measurement results of ¹ H-NMR related to the compound (D-973) obtained in Synthesis Example 9;

Fig. 10 is a graph showing the measurement results of ¹ H-NMR related to the compound (D-974) obtained in Synthesis Example 10;

Fig. 11 is a graph showing the measurement results of ¹ H-NMR related to the compound (D-998) obtained in Synthesis Example 11; and

Fig. 12 is a graph showing the results of ¹ H-MR measurements on the compound (D-1000) obtained in Synthesis Example 12.

Preferred Embodiments for Carrying Out the Invention

[0012]

The present invention provides a kind of aromatic amine derivative represented by following general formula (1) or general formula (2):

First, the arylamine derivative represented by the general formula (1) will be explained below.

[0013]

In the general formula (1), A ₁ to A ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 (preferably 1-20) carbon atoms, a substituted or unsubstituted alkyl group having 5-50 (preferably 5- 20) substituted or unsubstituted aryl groups with 1-50 (preferably 6-20) ring carbon atoms, substituted or unsubstituted aralkyl groups with 3-50 (preferably 5-12) ring carbon atoms ) substituted or unsubstituted cycloalkyl with ring carbon atoms, substituted or unsubstituted alkoxy with 1-50 (preferably 1-6) carbon atoms, 5-50 (preferably 5-18) A substituted or unsubstituted aryloxy group having 5-50 (preferably 5-18) ring carbon atoms, a substituted or unsubstituted arylamino group having 1-20 (preferably 1-6) ring carbon atoms A substituted or unsubstituted alkylamino group of carbon atoms, a substituted or unsubstituted heterocyclic group having 3-50 (preferably 3-20) ring carbon atoms, a 3-50 (preferably 3-20) carbon A substituted or unsubstituted silyl group or a halogen atom.

[0014]

Examples of substituted or unsubstituted alkyl represented by A _{to A} include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, Octyl, octadecyl, trichloromethyl, trifluoromethyl, etc.

Examples of substituted or unsubstituted aryl groups represented by A _{to A} include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, bi Phenyl, 4-methylbiphenyl, 4-ethylbiphenyl, 4-cyclohexylbiphenyl, terphenyl, 3,5-dichlorophenyl, naphthyl, 5-methylnaphthyl, Anthracenyl, pyrenyl, etc.

[0015]

Examples of substituted or unsubstituted aralkyl groups represented by A ₁ to A ₄ include benzyl, α,α-methylphenylbenzyl, triphenylmethyl, 1-phenethyl, 2-phenethyl , 1-phenylisopropyl, 2-phenylisopropyl, phenyl-tert-butyl, -naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α- Naphthylisopropyl, -α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthylethyl, 2-β-naphthylethyl, 1-β-naphthylisopropyl, 2 -β-naphthylisopropyl, α-phenoxybenzyl, α-benzyloxybenzyl, α,α-bistrifluoromethylbenzyl, 1-pyrrolylmethyl, 2-(1-pyrrole Base) ethyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl Benzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl Benzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro- 2-phenylisopropyl etc.

[0016]

Examples of the cycloalkyl represented by A ₁ to A ₄ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkoxy represented by _A1 to _A4 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, each Various pentyloxy groups, various hexyloxy groups, etc.

Examples of the aryloxy group represented by A ₁ to A ₄ include phenoxy, tolyloxy, naphthyloxy and the like.

Examples of arylamino groups listed in _A1 to _A4 include diphenylamino, xylylamino, isopropyldiphenylamino, tert-butyldiphenylamino, diisopropyldiphenylamino, di-tert- Butyldiphenylamino, dinaphthylamino, naphthylphenylamino, etc.

Examples of the alkylamino group represented by _A1 to _A4 include dimethylamino group, diethylamino group, dihexylamino group and the like.

Examples of the heterocyclic group represented by A _{to A} include imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline, Groups of isoquinoline, benzoquinone, pyrazoline, imidazolidine, piperidine, etc.

Examples of substituted or unsubstituted silyl groups represented by A _{to A} include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl group, propyldimethylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, etc.

Examples of the halogen atom represented by A ₁ to A ₄ include a fluorine atom, a chlorine atom, a bromine atom and the like.

[0017]

In the general formula (1), a, b, c and d each independently represent an integer of 0-5, preferably an integer of 0-3, more preferably an integer of 0-2.

When a, b, c, or d are each an integer of 2 or more, A ₁ to A ₄ may be the same or different from each other, and may be combined with each other to form a saturated or unsaturated ring; and in addition, a pair of A ₁ and A ₂ and a pair of _A3 and _A4 can combine with each other to form a saturated or unsaturated ring;

、苊等。Examples of the ring include cycloalkanes having 4 to 12 carbon atoms, such as cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, etc.; cycloalkenes having 4 to 12 carbon atoms, such as Cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc.; cycloalkadierie with 6-12 carbon atoms, such as cyclohexadiene, cycloheptadiene, cyclooctadiene alkenes, etc.; aromatic rings with 6-50 carbon atoms, such as benzene, naphthalene, phenanthrene, anthracene, pyrene,

, Acenaphthene, etc.

[0018]

In the general formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a primary or secondary alkyl group) having 1-50 (preferably 1-20) carbon atoms ), a substituted or unsubstituted aryl group having 5-50 (preferably 5-20) ring carbon atoms, a substituted or unsubstituted aralkyl group having 6-50 (preferably 6-20) ring carbon atoms , a substituted or unsubstituted cycloalkyl group having 3-50 (preferably 5-12) ring carbon atoms, a substituted or unsubstituted arylamino group having 5-20 (preferably 5-18) ring carbon atoms, A substituted or unsubstituted alkylamino group having 1-20 (preferably 1-10) carbon atoms, a substituted or unsubstituted heterocyclic group having 3-50 (preferably 3-20) ring carbon atoms or having A substituted or unsubstituted silyl group of 3-50 (preferably 3-20) carbon atoms; a pair of R ₁ and R ₂ and a pair of R ₃ and R ₄ can be combined with each other to form a saturated or unsaturated ring.

Specific examples of substituted or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, arylamino, alkylamino, heterocyclyl, silyl, and saturated or unsaturated rings represented by R _{to R} Examples are the same as those listed above in _A1 to _A4 .

It is particularly preferred that the alkyl groups represented by _R2 and _R4 are primary or secondary.

[0019]

In addition, examples of substituents of A ₁ to A ₄ and R ₁ to R ₄ include substituted or unsubstituted aryl groups having 5-50 (preferably 5-20) ring carbon atoms, aryl groups having 1-50 (preferably 1- 20) substituted or unsubstituted alkyl of carbon atoms, substituted or unsubstituted alkoxy having 1-50 (preferably 1-20) carbon atoms, 6-50 (preferably 6-20) A substituted or unsubstituted aralkyl group with ring carbon atoms, a substituted or unsubstituted aryloxy group with 5-50 (preferably 5-20) ring carbon atoms, a substituted or unsubstituted aryloxy group with 5-50 (preferably 5-20) A substituted or unsubstituted arylthio group having a ring carbon atom, a substituted or unsubstituted alkoxycarbonyl group having 1-50 (preferably 1-20) carbon atoms, an amino group, a halogen atom, a cyano group, a nitro group, Hydroxyl, carboxyl, etc.

[0020]

However, the case where all R ₁ to A ₄ are hydrogen atoms in the general formula (1) is excluded.

In addition, in the general formula (1), it is preferred that R and _/ or R _{independently} represent a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted alkyl group having 5-50 ring carbon atoms A substituted aryl group, a substituted or unsubstituted aralkyl group having 6-50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3-50 ring carbon atoms. Preferably R _and R _each independently represent a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms, a substituted or unsubstituted aryl group having 6-50 ring A substituted or unsubstituted aralkyl group of carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.

In addition, in the general formula (1), it is also preferred that _R1 to _R4 each independently represent a hydrogen atom, a substituted or unsubstituted arylamino group having 5-20 ring carbon atoms, a arylamino group having 1-20 carbon atoms, A substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group having 5-50 ring carbon atoms or a substituted or unsubstituted silyl group having 3-50 carbon atoms.

In addition, it is preferred that _R1 and/or _R3 represent methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or cyclohexyl.

In addition, it is preferred that _R2 and/or _R4 represent methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or cyclohexyl.

[0021]

Next, the arylamine derivative represented by the general formula (2) will be explained below:

[0022]

In the general formula (2), A ₅ to A ₈ each independently represent a substituted or unsubstituted alkyl group having 1-50 (preferably 1-20) carbon atoms, a substituted or unsubstituted alkyl group having 5-50 (preferably 5-20) A substituted or unsubstituted aryl group with ring carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-50 (preferably 5-12) ring carbon atoms or a substituted or unsubstituted cycloalkyl group with 3-50 (preferably 3-20) ring carbon atoms A substituted or unsubstituted heterocyclic group of carbon atoms;

In the general formula (2), R ₅ to R ₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 (preferably 1-20) carbon atoms, a substituted or unsubstituted alkyl group having 5-50 (preferably 5- 20) a substituted or unsubstituted aryl group with 6-50 (preferably 6-20) ring carbon atoms, a substituted or unsubstituted aralkyl group with 3-50 (preferably 5-12) ring carbon atoms ) substituted or unsubstituted cycloalkyl with ring carbon atoms, substituted or unsubstituted arylamino with 5-20 (preferably 5-12) ring carbon atoms, 1-20 (preferably 1-10) A substituted or unsubstituted alkylamino group of carbon atoms or a substituted or unsubstituted heterocyclic group having 3-50 (preferably 3-20) ring carbon atoms; a pair of R ₅ and R ₆ and a pair of R ₇ and R ₈ may combine with each other to form a saturated or unsaturated ring.

Specific examples of the groups represented by A ₅ to A ₈ and R ₅ to R ₈ in the general formula (2), specific examples of those substituents, and specific examples of those saturated or unsaturated rings are the same as the above general formula (1) Among them, A ₁ to A ₄ and R ₁ to R ₄ are the same as those listed examples.

Specific examples of the arylamine derivative represented by the general formula (1) or the general formula (2) will be illustrated below, but are not specifically limited thereto. Meanwhile, in the following compounds, Me represents a methyl group.

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

[table 17]

[Table 18]

[table 19]

[table 20]

[table 21]

[table 22]

[table 23]

[Table 24]

[Table 25]

[Table 26]

[table 27]

[Table 28]

[table 29]

[table 30]

[Table 31]

[table 32]

[table 33]

[table 34]

[Table 35]

[Table 36]

[table 37]

[table 38]

[table 39]

[table 40]

[table 41]

[table 42]

[table 43]

[table 44]

[table 45]

[table 46]

[table 47]

[table 48]

[table 49]

[table 50]

[table 51]

[table 52]

[table 53]

[table 54]

[table 55]

[table 56]

[table 57]

[table 58]

[table 59]

[table 60]

[table 61]

[table 62]

[table 63]

[table 64]

[Table 65]

[Table 66]

[Table 67]

[Table 68]

[Table 69]

[Table 70]

[table 71]

[table 72]

[table 73]

[Table 74]

[Table 75]

[Table 76]

[Table 77]

[Table 78]

[Table 79]

[table 80]

[Table 81]

[Table 82]

[Table 83]

[Table 84]

[Table 85]

[table 86]

[table 87]

[Table 88]

[table 89]

[0125]

In the arylamine derivatives of the present invention, since the aryl (especially benzene ring), alkyl, cycloalkyl or heterocyclic group is connected with the diaminosugar structure as the luminescent center, the association between the compounds is prevented ( association), resulting in a longer service life. In addition, due to the bulky substituents and The coupling of the backbone structure increases the steric repulsion of the amine structure and thus also further extends its service life.

In addition, the arylamine derivatives have strong fluorescence in the solid state, are excellent in electric field light emission, and can make the fluorescence quantum efficiency as high as 0.3 or above. In addition, the arylamine derivatives of the present invention not only exhibit excellent ability to inject or transport holes from metal electrodes or organic thin film layers, but also exhibit excellent ability to inject or transport electrons from metal electrodes or organic thin film layers, Therefore, it can generally be used as a light-emitting material, especially as a doping material for an organic EL device. Besides, the arylamine derivatives of the present invention can be used together with other hole transporting substances, electron transporting substances or doping substances.

[0126]

The organic EL device of the present invention comprises one or more organic thin film layers sandwiched between an anode and a cathode. In the case of a one-layer type, a light-emitting layer as an organic thin film layer is sandwiched between an anode and a cathode. The light emitting layer contains the luminescent substance, and may further contain a hole injecting substance and an electron injecting substance for transporting holes injected from the anode or electrons injected from the cathode to the luminescent substance. The arylamine derivatives of the present invention have the properties of enhancing light emission, excellent hole injection properties and hole transport properties, and also have excellent electron injection properties and electron transport properties, therefore, they can be used as luminescent substances in the light emitting layer and doping substances.

In the organic EL device of the present invention, the light emitting layer contains the arylamine derivative of the present invention in a weight ratio of preferably 0.1-20%, more preferably 1-10% by weight. In addition, the arylamine derivatives of the present invention not only exhibit very high fluorescence quantum efficiency, but also exhibit high hole transport ability and electron transport ability, and also have the ability to form a uniform thin film, so it can be obtained only by the arylamine Derivatives form the light emitting layer.

On the other hand, when the organic EL device of the present invention comprises two or more organic thin film layers having at least one light-emitting layer sandwiched between an anode and a cathode, the organic thin film layers preferably contain An inventive organic layer of arylamine derivatives, the organic layer is between the anode and the light emitting layer. Such an organic layer may be a hole injection layer, a hole transport layer, or the like.

[0127]

In addition, when the arylamine derivatives of the present invention are used as doping substances, it is preferable to use at least one anthracene derivative selected from the following general formula (3), anthracene derivatives of the following general formula (4) and the following general formula ( 5) Pyrene derivatives as the host material.

[0128]

In the general formula (3), _X1 and _X2 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted alkyl group having 5-50 ring carbon atoms Aryl, substituted or unsubstituted aralkyl having 6-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 3-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 1-50 ring carbon atoms A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group having 5-50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5-50 ring carbon atoms, having 1 -substituted or unsubstituted alkylamino with 20 carbon atoms, substituted or unsubstituted heterocyclic group or halogen atom with 5-50 ring carbon atoms; e or f each independently represent an integer of 0-4; When e or f is an integer of 2 or more, _X1 to _X2 may be the same as or different from each other.

Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group with 5-50 ring carbon atoms or a substituted or unsubstituted heterocyclic group with 5-50 ring carbon atoms; Ar ₁ or Ar ₂ At least one represents a substituted or unsubstituted aryl group having fused rings and having 10-50 ring carbon atoms; m represents an integer of 1-3. When m is an integer of 2 or more, the groups in the above brackets [ ] may be the same as or different from each other.

Specific examples and substituents of X ₁ , X ₂ , Ar ₁ and Ar ₂ are the same as those explained in the above general formula (1).

[0129]

[0130]

In the general formula (4), X ₁ to X ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted alkyl group having 5-50 ring carbon atoms Aryl, substituted or unsubstituted aralkyl having 6-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 3-50 ring carbon atoms, substituted or unsubstituted cycloalkyl having 1-50 carbon atoms Substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy with 5-50 ring carbon atoms, substituted or unsubstituted arylamino with 5-50 ring carbon atoms, 1- A substituted or unsubstituted alkylamino group with 20 carbon atoms, a substituted or unsubstituted heterocyclic group or a halogen atom with 5-50 ring carbon atoms; e, f and g each independently represent an integer of 0-4 . When e, f or g is an integer of 2 or more, X ₁ , X ₂ and X ₃ may be the same as or different from each other.

Ar ₁ represents a substituted or unsubstituted aryl group having a fused ring and having 10-50 ring carbon atoms, Ar ₃ represents a substituted or unsubstituted aryl group having 5-50 ring carbon atoms; n represents 1 An integer of -3. When n is an integer of 2 or more, the groups in the above brackets [ ] may be the same as or different from each other.

Specific examples and substituents of X ₁ to X ₃ , Ar ₁ and Ar ₃ are the same as those explained in the above general formula (1).

[0131]

Specific examples of the anthracene derivatives represented by the general formulas (3) and (4) are illustrated below, but are not particularly limited thereto.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

In the general formula (5), Ar ₅ and Ar ₆ each represent a substituted or unsubstituted aryl group having 6-50 ring carbon atoms;

L _and L _each independently represent substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted fluorenylene or substituted or unsubstituted dibenzosilolylene;

s represents an integer of 0-2, p represents an integer of 1-4, q represents an integer of 0-2, and r represents an integer of 0-4; and

L ₁ or Ar ₅ is connected to any position of the 1-5 position of pyrene, and L ₂ and Ar ₆ are connected to any position of its 6-10 position,

However, when p+r is an even number, Ar ₅ , Ar ₆ , L ₁ and L ₂ satisfy the following requirement (1) or requirement (2):

(1) Ar ₅ ≠Ar ₆ and/or L ₁ ≠L ₂ (where ≠ means that each group has a different structure)

(2) When Ar ₅ =Ar ₆ and L ₁ =L ₂ ,

(2-1) s≠q and/or p≠r, or

(2-2) When s=q and p=r,

(2-2-1) L ₁ and L ₂ or pyrene are each bound to different positions of Ar ₅ and Ar ₆ , respectively, or (2-2-2) L ₁ and L ₂ or pyrene are each bound to Ar ₅ and Ar _{6 respectively} binding at the same position, but excluding the case when both L ₁ and L ₂ or Ar ₅ and Ar ₆ are linked to their 1 and 6 positions or their 2 and 7 positions.

Specific examples and substituents of Ar ₅ , Ar ₆ , L ₁ and L ₂ are the same as those explained above for the aforementioned general formula (1).

[0138]

Specific examples of the pyrene derivative represented by the general formula (5) are illustrated below, but not specifically limited thereto.

[0139]

[0140]

Examples of multilayer organic EL devices include those having a multilayer structure (such as anode/hole injection layer/light emission layer/cathode), (anode/light emission layer/electron injection layer/cathode), and (anode/hole injection layer //Light Emissive Layer/Electron Injection Layer/Cathode) those devices.

The multilayer may optionally contain conventionally known substances such as desired light-emitting substances, doping substances, hole-injecting substances and electron-injecting substances in addition to the aromatic amine derivatives of the present invention. An organic EL device having such a multilayer structure can prevent reductions in luminance and lifetime due to quenching. The light-emitting substance, dopant substance, hole injection substance, and electron injection substance may be used in combination with each other, if necessary. The use of dopant species enables the resulting device to improve the brightness and efficiency of light emission, further emitting a red or blue light. In addition, in the organic EL device of the present invention, the hole injection layer, the light emission layer, and the electron injection layer may each have a multilayer structure including 2 or more layers. In these cases, the layer that injects holes from the electrode is called a hole injection layer, while the layer that accepts holes from the hole injection layer and transports the holes to the light emitting layer is called a hole transport layer. layer. Also, a layer that injects electrons from an electrode is called an electron injection layer, and a layer that transports and accepts electrons from the electron injection layer and a layer that transports electrons to a light-emitting layer is called an electron transport layer. Each of the layers described above can be selectively used depending on various factors such as the energy level of the substance used, thermal resistance, and adhesion to an organic thin film layer or a metal electrode.

[0141]

、十环烯、蔻(coronene)、四苯基环戊二烯、五苯基环戊二烯、芴、螺芴、9，10-二苯基蒽、9，10-二(苯基-乙炔基)蒽、1，4-二(9’-乙炔基蒽基)苯基及其这些化合物的衍生物；有机金属复合物，如三(8-喹啉酚根合(quinolinolat))铝、二(2-甲基-8-喹啉酚根合)-4-(苯基酚根合(phenolinat))铝等；三芳基胺衍生物、苯乙烯胺衍生物、二苯乙烯衍生物、香豆素衍生物、吡喃衍生物、嗪酮衍生物、苯并噻唑衍生物、苯并唑衍生物、苯并咪唑衍生物、吡嗪衍生物、肉桂酸酯衍生物、二酮基吡咯并吡咯衍生物、吖啶酮衍生物、喹吖啶酮(quinacridon)衍生物等；但不具体限定于此。Examples of main substances or dopant substances that can be used in the light-emitting layer together with the aromatic amine derivatives of the present invention include condensed polyaromatic compounds such as naphthalene, phenanthrene, rubrene, anthracene, naphthacene, pyrene, perylene,

, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, 9,10-diphenylanthracene, 9,10-bis(phenyl-acetylene base) anthracene, 1,4-bis(9'-ethynyl anthracenyl)phenyl and derivatives of these compounds; organometallic complexes such as tris(8-quinolinolat)aluminum, di (2-methyl-8-quinoline phenolate)-4-(phenylphenolate (phenolinat)) aluminum, etc.; triarylamine derivatives, styrylamine derivatives, stilbene derivatives, coumarin Vine derivatives, pyran derivatives, oxazinone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, diketopyrrolo Pyrrole derivatives, acridone derivatives, quinacridon derivatives, etc.; but not particularly limited thereto.

[0142]

The hole-injecting substance is preferably composed of a compound that has a good hole-transporting ability and has an ability to accept holes injected from the anode and an excellent ability to inject holes onto the light-emitting layer or the light-emitting substance, preventing The excited particles generated in the light emitting layer move to the electron injection layer or the electron injection substance, and exhibit excellent thin film forming ability. Specific examples of the hole injecting substance include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazoles, oxadiazoles, triazoles, imidazoles, imidazolinones, imidazolethiones (thione), pyridine Azoline, pyrazolone, tetrahydroimidazole, hydrazone, acylhydrazone, polyaryl alkanes, stilbene, butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine, di Amine-type triphenylamine and its derivatives, as well as polyvinylcarbazole, polysilane, and high molecular materials such as conductive polymers, but not specifically limited thereto.

[0143]

Among those hole injecting substances used in the organic EL device of the present invention, more effective hole injecting substances are aromatic tertiary amine derivatives and phthalocyanine derivatives.

Specific examples of aromatic tertiary amine derivatives include triphenylamine, trimethylaniline, tolyldiphenylamine, N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1' -Biphenyl-4,4'-diamine, N,N,N',N'-(4-methylphenyl)-1,1'-phenyl-4,4'-diamine, N, N,N',N'-(4-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-binaphthalene Base-1,1'-biphenyl-4,4'-diamine, N,N'-(methylphenyl)-N,N'-(4-n-butylphenyl)-phenanthrene-9, 10-diamine, N,N-bis(4-di-4-tolylaminophenyl)-4-phenyl-cyclohexane and oligomers and polymers with these aromatic tertiary amine backbones, but Not specifically limited thereto.

[0144]

Specific examples of phthalocyanine (Pc) derivatives include phthalocyanine derivatives such as _H2Pc , CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, _Cl2SiPc , (HO) AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc, and naphthalocyanine derivatives, but are not particularly limited thereto.

In the organic EL device of the present invention, between the light-emitting layer and the anode, it is also preferable to form the above-mentioned hole transport layer or hole injection layer containing, for example, those aromatic tertiary amine derivatives and/or phthalocyanine derivatives. layer by layer.

[0145]

The electron-injecting substance is preferably composed of a compound having a good electron-transporting ability and an ability to accept electrons injected from the cathode and a superior ability to inject electrons onto the light-emitting layer or the light-emitting substance, which can prevent the light-emitting layer from The generated excited particles move to the hole injection layer and exhibit excellent thin film forming ability. Specific examples of the electron injecting substance include fluorenone, anthraquinodimethane, dibenzoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, Anthrone and its derivatives, but not specifically limited thereto. In addition, to enhance the sensitivity thereof, an electron accepting substance and an electron donating substance may be added to the hole injecting substance and the electron injecting substance, respectively.

[0146]

Among these electron injecting substances used in the organic EL device of the present invention, more effective electron injecting substances are metal complex compounds and five-membered ring derivatives having nitrogen atoms.

Specific examples of the metal complex compound include lithium 8-quinoline phenate, bis(8-quinoline phenate) zinc, bis(8-quinoline phenate) copper, bis(8-quinoline phenate) Al) Manganese, Tris(8-quinoline phenate) Aluminum, Tris(2-Methyl-8-quinoline phenate) Aluminum, Tris(8-quinoline phenate) Gallium, Bis(10-Hydroxy Benzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinolato)gallium chloride, bis( 2-methyl-8-quinoline phenolate) (o-cresolato (o-cresolato)) gallium, two (2-methyl-8-quinoline phenolate) (1-naphtholate ( naphtholato))aluminum, bis(2-methyl-8-quinolinolate)(2-naphtholato)gallium, but not specifically limited thereto.

The five-membered ring derivative having a nitrogen atom is preferably a derivative of oxazole, thiazole, oxadiazole, thiadiazole or triazole. Specific examples of the nitrogen-containing five-membered ring derivative include 2,5-bis(1-phenyl)-1,3,4-oxazole, dimethyl POPOP, 2,5-bis(1-phenyl )-1,3,4-thiazole, 2,5-bis(1-phenyl)-1,3,4-oxadiazole, 2-(4'-tert-butylphenyl)-5-(4" -biphenyl)-1,3,4-oxadiazole, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole, 1,4-bis[2-(5-benzene oxadiazolyl)]benzene, 1,4-bis[2-(5-phenyloxadiazolyl)-4-tert-butylbenzene], 2-(4'-tert-butylphenyl)-5 -(4”-biphenyl)-1,3,4-thiadiazole, 2,5-bis(1-naphthyl)-1,3,4-thiadiazole, 1,4-bis[2- (5-Phenylthiadiazolyl)]benzene, 2-(4'-tert-butylphenyl)-5-(4"-biphenyl)-1,3,4-triazole, 2,5- Bis(1-naphthyl)-1,3,4-triazole and 1,4-bis[2-(5-phenyltriazolyl)]benzene, but not specifically limited thereto.

[0147]

In the organic EL device of the present invention, in addition to the arylamine derivative represented by the general formula (1), the light-emitting layer may optionally contain at least one substance selected from the group consisting of light-emitting substances, doping substances, Hole-injecting substances and electron-injecting substances. In order to enhance the stability against temperature, humidity, air, etc., the organic EL device of the present invention may also have a protective layer on its surface, or its entire part may be protected with silicone oil, resin, etc.

The anode of the organic EL device of the present invention may suitably be made of a conductive substance having a free energy greater than 4 eV. Examples of conductive substances of the anode include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium and alloys thereof, metal oxides used as ITO substrates or NESA substrates (such as tin oxide and indium oxide), and organic conductive resins such as polythiophene and polypyrrole. The cathode of the organic EL device of the present invention can be suitably made of a conductive substance having a free energy of 4 eV or less. Examples of the conductive substance of the cathode include magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride and alloys thereof, but are not particularly limited thereto. Typical examples of the alloy include alloys of magnesium and silver, alloys of magnesium and indium, and alloys of lithium and aluminum, but are not particularly limited thereto. The ratio between the constituent metals in the alloy can be controlled, and the ratio is suitably determined depending on the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, and the like. The anode and cathode may be composed of two or more layers, if desired.

[0148]

At least one surface of the organic EL device of the present invention preferably exhibits sufficient transparency in the wavelength range of light emission to enhance its light emission efficiency. In addition, the substrate of the device is also preferably transparent. The transparent electrode is formed by using the above-mentioned conductive substance through vapor deposition method, sputtering method, etc., so as to ensure the required light transmittance. The electrodes disposed on the light emitting surface of the device preferably have a light transmittance of 10% or more. The substrate is not particularly limited as long as it has good mechanical and thermal strength and good light transmittance. Examples of the substrate include glass substrates and transparent resin films. Specific examples of the transparent resin film include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyethylene Butyral (butyral), nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexa Fluoropropylene copolymers, polychlorotrifluoroethylene, polyvinylidene fluoride, polyesters, polycarbonates, polyurethanes, polyimides, polyetherimides, and polypropylene.

[0149]

Each layer of the organic EL device of the present invention can be formed by a dry film forming method (such as vacuum coating method, sputtering method, plasma and ion plating method) or a wet film forming method (such as spin coating method, dipping method and flow coating method) )form. The thickness of each layer is not particularly limited, but should be adjusted to an appropriate range. When the thickness is too large, a large voltage must be applied to the device to achieve a predetermined light output, resulting in a decrease in light emission efficiency. On the other hand, when the thickness is too small, pinholes are easily formed in each layer, so that sufficient brightness of light emission cannot be obtained even if an electric field is applied thereon. Suitable thicknesses of the layers generally range from 5 nm to 10 μm, preferably from 10 nm to 0.2 μm.

In the wet film forming method, materials constituting each layer are dissolved or dispersed in a suitable solvent such as ethanol, chloroform, tetrahydrofuran, and dioxane to form a thin film thereof. The solvent used to form each layer is not particularly limited. Suitable resins or additives may also be added to each organic thin film layer to improve film-forming properties, prevent pinhole formation in the resulting film, and the like. Examples of resins used for the above purpose include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethylmethacrylate, polyacrylic acid Methyl esters and celluloses and their copolymers, photoconductive resins such as poly-N-vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of additives include antioxidants, ultraviolet absorbers, and plasticizers.

[0150]

The organic EL device of the present invention is suitably used, for example, as a flat panel light emitting element, such as a flat panel display of a wall-mounted television, etc., a light source of a copier, a printer, a liquid crystal display, and the back of a measuring instrument, a display panel, a marker light, etc. light source. In addition, the substance of the present invention can be used not only in organic EL devices but also in other applications such as electrophotographic elements, photoelectric converter elements, solar cells, image sensors, and the like.

Example

[0151]

The present invention is described in detail by referring to the following examples.

Synthesis Example 1 (Synthesis of Chemical Compound (4))

(1-1) Synthesis of 2-bromo-6-methylnaphthalene

Under argon flow, add 32g (90mmol) of trifluoromethanesulfonate-6-bromo-2-naphthyl ester, 3.6g (5% mole) of dichloride ( Diphenylphosphinoferrocene)palladium, 7.8g (90mmol) of lithium bromide and 100mL of dry tetrahydrofuran were then cooled to -20°C. After slowly adding 90 mL (90 mmol, 1 mol/L (tetrahydrofuran)) of methylmagnesium bromide to the flask, the resulting solution was stirred while heating at 80° C. for 4 hours. After the reaction was terminated, 100 mL of dilute hydrochloric acid was added to the reaction solution, and the organic layer was separated, washed with sodium bicarbonate solution and sodium chloride solution, and then dried over magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=90/10) to obtain 9.4 g of the target compound (white crystals) (yield: 47%) .

(1-2) Synthesis of 2-(6-methyl-2-naphthyl)benzaldehyde

Under argon flow, add 6.6g (30mmol) of 2-bromo-6-methylnaphthalene, 5.4g (36mmol) of 2-formylphenylboronic acid, 0.7g ( 0.6mmol) of tetrakis(triphenylphosphine)palladium, 45mL of 2N aqueous sodium carbonate and 90mL of dimethoxyethane, and heated the resulting solution to reflux for 8 hours. After the reaction was terminated, 100 mL of water was added to the reaction solution, and the organic layer was separated, washed with a sodium chloride solution, and then dried over magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=60/40) to obtain 6.7 g of the target compound (white crystals) (yield: 91%) .

[0152]

Synthesis of (1-3) 2-((2-methoxyvinyl)phenyl)-6-methylnaphthalene

Under argon flow, add 13.7g (55mmol) of 2-(6-methyl-2-naphthyl)benzaldehyde, 21g (61mmol) of (methoxy methyl) triphenylphosphonium, 7.5 g (67 mmol) of potassium tert-butoxide and 250 mL of dry tetrahydrofuran, and the resulting solution was stirred overnight at room temperature. After the reaction was terminated, 100 mL of water was added to the reaction solution, and the organic layer was separated, followed by drying with magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=10/90) to obtain 12.8 g of the target compound (white crystals) (yield: 84%) .

(1-4)2-Methyl Synthesis

Under argon flow, add 12.8 g (46 mmol) of 2-((2-methoxyvinyl)phenyl)-6-methylnaphthalene, a few drops of formic acid and 100 mL of dry dichloromethane, and the resulting solution was stirred at room temperature for 8 hours. After the reaction was terminated, 100 mL of sodium bicarbonate solution was added to the reaction solution, and the crystals were separated by filtration. The obtained crude product was washed with water and methanol, and then vacuum-dried at a temperature of 50° C. for 8 hours to obtain 8.2 g of the target compound (white crystals) (yield: 73%).

[0153]

的合成(1-5) 2-Methyl-6,12-dibromo

Synthesis

、14.5g(81mmol)的N-溴琥珀酰亚胺和400mL N，N-二甲基甲酰胺，然后将得到的溶液在室温下搅拌一夜。反应终止后，向该反应溶液中加入300mL水，过滤分离晶体。将得到的粗产物用水和甲醇洗涤，然后用100mL甲苯重结晶，得到8.8g目标化合物(白色晶体)(收率：65％)。Under argon flow, add 8.2g (34mmol) of 2-methyl

, 14.5 g (81 mmol) of N-bromosuccinimide and 400 mL of N,N-dimethylformamide, and then the resulting solution was stirred at room temperature overnight. After the reaction was terminated, 300 mL of water was added to the reaction solution, and the crystals were separated by filtration. The obtained crude product was washed with water and methanol, and then recrystallized from 100 mL of toluene to obtain 8.8 g of the target compound (white crystals) (yield: 65%).

(1-6) Synthesis of chemical compound (4)

Under argon flow, add 4.0 g (10 mmol) of 2-methyl-6,12-dibromo to a 300 mL three-necked flask equipped with a condenser , 5.6g (25mmol) of two (3,4-dimethylphenyl) amine, palladium acetate of O.03g (1.5% mole), tri-tert-butylphosphine of O.06g (3% mole), 2.4g (25 mmol) of sodium tert-butoxide and 100 mL of dry toluene were heated at 100° C., and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 5.8 g of light yellow powder. According to the results of Field Desorption Mass Spectrum (FD-MS) measurement, the pale yellow powder was compound (4) (yield: 85%).

The results of the ¹ H-NMR spectrum of compound (4) obtained by using dichloromethane as a solvent and measured by DRX-500 (trade name: manufactured by Brucker Optics Inc.) are shown in FIG. 1 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (4) in toluene solvent are 400nm and 456nm, respectively.

[0154]

Synthesis Example 2 (Synthesis of Compound (9))

(2-1) 2-isopropyl-6,12-dibromo Synthesis

The target compound was obtained in a similar manner from step (1-1) to step (1-5) of Synthesis Example 1, but using isopropylmagnesium bromide instead of methylmagnesium bromide in step (1-1).

(2-2) Synthesis of compound (9)

Under argon flow, add 4.2 g (10 mmol) of 2-isopropyl-6,12-dibromo to a 300 mL three-necked flask equipped with a condenser , 5.6g (25mmol) of 4-isopropylphenyl-p-toluidine, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) Sodium tert-butoxide and 100 mL of dry toluene were heated at 100°C, and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.4 g of light yellow powder. The obtained product was determined to be compound (9) according to FD-MS measurement (yield: 90%).

The results of the ¹ H-NMR spectrum of Compound (9) obtained by measuring with DRX-500 (trade name: manufactured by Brucker Optics Inc.) using dichloromethane as a solvent are shown in FIG. 2 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (9) in toluene solvent are 407nm and 453nm, respectively.

[0155]

Synthesis Example 3 (Synthesis of Chemical Compound (20))

(3-1) Synthesis of 2-bromo-6-isopropylnaphthalene

Under argon flow, add 32g (90mmol) of trifluoromethanesulfonate-6-bromo-2-naphthyl ester, 3.6g (5% mole) of dichloride ( Diphenylphosphinoferrocene)palladium, 7.8g (90mmol) of lithium bromide and 100mL of dry tetrahydrofuran were then cooled to -20°C. 90 mL (90 mmol, 1 mol/L (tetrahydrofuran)) of isopropylmagnesium bromide was slowly added to the flask, and the resulting solution was stirred under heating at 80° C. for 4 hours. After the reaction was terminated, 100 mL of dilute hydrochloric acid was added to the reaction solution, and the organic layer was separated, washed with sodium bicarbonate solution and sodium chloride solution, and then dried over magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=90/10) to obtain 9.4 g of the target compound (white crystals) (yield: 33%) .

(3-2) Synthesis of 6-isopropylnaphthalene-2-boronic acid

Under argon flow, add 9.4 g (38 mmol) of 2-bromo-6-isopropylnaphthalene, 100 mL of dry ether and 50 mL of dry toluene to a 500 mL three-necked flask equipped with a condenser, and then cool the resulting solution to -40°C. 25 mL (40 mmol, 1.58 M (n-hexane)) of n-butyllithium was slowly added dropwise to the flask, and the resulting solution was stirred at -20°C for 2 hours. Then the solution was cooled to -40°C, and then 26 mL (114 mmol) of triisopropyl borate was slowly added dropwise, and the resulting solution was stirred overnight at room temperature. After the reaction was terminated, 100 mL of dilute hydrochloric acid was added to the reaction solution, and the organic layer was separated, washed with a sodium chloride solution, and then dried over magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the obtained crude product was washed with 100 mL of toluene to obtain 5.0 g of the target compound (white crystals) (yield: 63%).

[0156]

(3-3) Synthesis of 5-isopropyl-2-(6-isopropyl-2-naphthyl)benzaldehyde

Under argon flow, add 4.4g (27mmol) of 2-hydroxyl-5-isopropylbenzaldehyde, 11.2g (40mmol) of trifluoromethanesulfonic anhydride, 6mL (80mmol) to a 500mL three-necked flask equipped with a condenser ) of pyridine and 100 mL of dichloromethane, and then the resulting solution was stirred at room temperature for 2 hours. After the reaction was terminated, the product was separated by filtration, and the obtained crude product was washed with hexane and dichloromethane, and then dried in vacuum at 50° C. for 8 hours to obtain 6.0 g of 2-formyl-4-isopropylphenyltris Flate (white crystals) (yield: 75%). Next, under argon flow, 5.9 g (20 mmol) of 2-formyl-4-isopropylphenyl trifluoromethanesulfonate, 4.7 g (22 mmol) of 6-isopropylnaphthalene-2-boronic acid, 1.1 g (1 mmol) of tetrakis(triphenylphosphine)palladium, 30 mL of 2N aqueous sodium carbonate and 40 mL of dimethoxyethane, and the resulting solution was heated to reflux for 8 hours. After the reaction was terminated, 100 mL of water was added to the reaction solution, and the organic layer was separated, washed with a sodium chloride solution, and then dried over magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=60/40) to obtain 4.4 g of the target compound (white crystals) (yield: 70%) .

Synthesis of (3-4) 2-isopropyl-6-(4-isopropyl-2-(2-methoxyvinyl)phenyl)naphthalene

Under argon flow, add 4.4g (14mmol) of 5-isopropyl-2-(6-isopropyl-2-naphthyl) benzaldehyde, 5.1g (15mmol) to a 500mL three-necked flask equipped with a condenser ) of (methoxymethyl)triphenylphosphonium chloride, 1.7 g (15 mmol) of potassium tert-butoxide and 100 mL of dry tetrahydrofuran, and the resulting solution was stirred overnight at room temperature. After the reaction was terminated, 100 mL of water was added to the reaction solution, and the organic layer was separated, followed by drying with magnesium sulfate. The solvent was distilled off using a rotary evaporator, and the resulting crude product was purified by column chromatography (silica gel, hexane/dichloromethane=10/90) to obtain 4.3 g of the target compound (white crystals) (yield: 90%) .

[0157]

(3-5)2,8-diisopropyl Synthesis

Under argon flow, add 4.3g (12mmol) of 2-isopropyl-6-(4-isopropyl-2-(2-methoxyvinyl)benzene to a 300mL three-necked flask equipped with a condenser base) naphthalene, a few drops of formic acid and 50 mL of dry dichloromethane, and the resulting solution was stirred at room temperature for 8 hours. After the reaction was terminated, 100 mL of sodium bicarbonate solution was added to the reaction solution, and the crystals were separated by filtration. The obtained crude product was washed with water and methanol, and then vacuum-dried at a temperature of 50° C. for 8 hours to obtain 3.5 g of the target compound (white crystals) (yield: 90%).

(3-6) 2,8-diisopropyl-6,12-dibromo Synthesis

Under argon flow, add 3.5 g (12 mmol) of 2,8-diisopropyl to a 500 mL three-necked flask equipped with a condenser , 5.3 g (30 mmol) of N-bromosuccinimide and 20 ml of N, N-dimethylformamide, and then the resulting solution was stirred overnight at room temperature. After the reaction was terminated, 300 mL of water was added to the reaction solution, and the crystals were separated by filtration. The obtained crude product was washed with water and methanol, and then recrystallized from 100 mL of toluene to obtain 4.7 g of the target compound (white crystals) (yield: 80%).

(3-7) Synthesis of chemical compound (20)

、5.6g(25mmol)的4-异丙基苯基对甲苯胺、0.03g(1.5％摩尔)的乙酸钯、0.06g(3％摩尔)的三叔丁基膦、2.4g(25mmol)的叔丁醇钠和100mL干燥的甲苯，在l00℃温度加热下，将得到的溶液搅拌一夜。反应终止后，过滤分离沉淀的晶体，用50mL甲苯和100mL甲醇洗涤，得到6.6g浅黄色粉末。根据FD-MS测定，确定得到的产物为化合物(20)(收率：88％)。Under argon flow, add 4.7 g (10 mmol) of 2,8-diisopropyl-6,12-dibromo to a 300 mL three-necked flask equipped with a condenser

, 5.6g (25mmol) of 4-isopropylphenyl-p-toluidine, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) of tert- Sodium butoxide and 100 mL of dry toluene were heated at 100°C, and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.6 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (20) (yield: 88%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used to measure the results of the ¹ H-NMR spectrum of the obtained compound (20), as shown in FIG. 3 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (20) in toluene solvent are 407nm and 450nm, respectively.

[0158]

Synthesis Example 4 (Synthesis of Compound (23))

(4-1) 2-tert-butyl-8-isopropyl-6,12-dibromo Synthesis

In a similar manner from Synthetic Example 3 step (3-1) to step (3-6), but replace 2-hydroxyl-5- Cumyl benzaldehyde, to obtain the target compound.

(4-2) Synthesis of compound (23)

Under argon flow, add 4.8 g (10 mmol) of 2-tert-butyl-8-isopropyl-6,12-dibromo to a 300 mL three-necked flask equipped with a condenser , 5.6g (25mmol) of two (3,4-dimethylphenyl) amine, palladium acetate of O.03g (1.5% mole), tri-tert-butylphosphine of 0.06g (3% mole), 2.4g ( 25 mmol) of sodium tert-butoxide and 100 mL of dry toluene were heated at 100° C., and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.9 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (23) (yield: 90%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement, and the results of the ¹ H-NMR spectrum of the obtained compound (23) are shown in FIG. 4 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (23) in toluene solvent are 409nm and 453nm, respectively.

[0159]

Synthesis Example 5 (Synthesis of Compound (25))

6.3g(25mmol)的二(3，4-二甲基苯基)胺、0.03g(1.5％摩尔)的乙酸钯、O.06g(3％摩尔)的三叔丁基膦、2.4g(25mmol)的叔丁醇钠和100mL干燥的甲苯，在100℃温度加热下，将得到的溶液搅拌一夜。反应终止后，过滤分离沉淀的晶体，用50mL甲苯和100mL甲醇洗涤，得到6.8g浅黄色粉末。根据FD-MS测定，确定得到的产物为化合物(25)(收率：88％)。Under argon flow, in the 300mL three-necked flask that is equipped with condenser tube, add the 2-isopropyl-6 that 12-dibromo that obtains in the step (2-1) of the synthetic example 2 of 4.2g (10mmol)

6.3g (25mmol) of two (3,4-dimethylphenyl) amines, 0.03g (1.5% mole) of palladium acetate, O.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol% mole) ) sodium tert-butoxide and 100 mL of dry toluene, and the resulting solution was stirred overnight under heating at 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.8 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (25) (yield: 88%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement, and the results of the ¹ H-NMR spectrum of the obtained compound (25) are shown in FIG. 5 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (25) in toluene solvent are 415nm and 459nm, respectively.

[0160]

Synthesis Example 6 (Synthesis of Compound (39))

Under argon flow, add 4.2g (10mmol) of 2-isopropyl-6,12-dibromide obtained in the step (2-1) of Synthesis Example 2 to a 300mL three-necked flask equipped with a condenser 6.7g (25mmol) of two (2-naphthyl) amines, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) of tert-butyl alcohol Sodium and 100 mL of dry toluene were added, and the resulting solution was stirred overnight under heating at 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.8 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (39) (yield: 85%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement, and the results of the ¹ H-NMR spectrum of the obtained compound (39) are shown in FIG. 6 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (39) in toluene solvent are 408nm and 452nm, respectively.

[0161]

Synthesis Example 7 (Synthesis of Compound (57))

的合成(7-1) 2-tert-butyl-6,12-dibromo

Synthesis

The target compound was obtained in a similar manner from Step (1-1) to Step (1-5) of Synthesis Example 1, but tert-butylmagnesium bromide was used instead of methylmagnesium bromide in step (1-1).

(7-2) Synthesis of compound (57)

Under argon flow, add 4.4 g (10 mmol) of 2-tert-butyl 6,12-dibromide to a 300 mL three-necked flask equipped with a condenser , 5.6g (25mmol) of two (3,4-dimethylphenyl) amine, 0.03g (1.5% mol) of palladium acetate, 0.06g (3 mol% mol) of tri-tert-butylphosphine, 2.4g (25mmol ) sodium tert-butoxide and 100 mL of dry toluene, and the resulting solution was stirred overnight under heating at 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.5 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (57) (yield: 90%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc.) was used for measurement. The results of the ¹ H-NMR spectrum of the obtained compound (57) are shown in FIG. 7 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (57) in toluene solvent are 410 nm and 456 nm, respectively.

[0162]

Synthesis Example 8 (Synthesis of Compound (95))

Under argon flow, add 4.0g (10mmol) of 2-methyl-6,12-dibromo that is obtained in the step (1-5) of Synthetic Example 1 to the 300mL three-necked flask that is equipped with condenser tube , 8.3g (25mmol) of two (4-cyclohexylphenyl) amine, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) of tertiary Sodium butoxide and 100 mL of dry toluene were heated at 100° C., and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 6.3 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (95) (yield: 70%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement, and the results of the ¹ H-NMR spectrum of the obtained compound (95) are shown in FIG. 8 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (95) in toluene solvent are 406 nm and 454 nm, respectively.

[0163]

Synthesis Example 9 (Synthesis of Compound (D-973))

、2.7g(25mmol)的N-甲基苯胺、0.03g(1.5％摩尔)的乙酸钯、O.06g(3％摩尔)的三叔丁基膦、2.4g(25mmol)的叔丁醇钠和100mL干燥的甲苯，在100℃温度加热下，将得到的溶液搅拌一夜。反应终止后，过滤分离沉淀的晶体，用50mL甲苯和100mL甲醇洗涤，得到2.2g白色粉末。根据FD-MS测定，确定得到的产物为化合物(D-973)(收率：50％)。Under argon flow, add 3.8 g (10 mmol) of 6,12-dibromo

, 2.7g (25mmol) of N-methylaniline, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) of sodium tert-butoxide and 100 mL of dry toluene was heated at 100°C, and the resulting solution was stirred overnight. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 2.2 g of white powder. According to FD-MS measurement, it was confirmed that the obtained product was compound (D-973) (yield: 50%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement. The results of the ¹ H-NMR spectrum of the obtained compound (D-973) are shown in FIG. 9 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of the compound (D-973) in toluene solvent were 373 nm and 440 nm, respectively.

[0164]

Synthesis Example 10 (Synthesis of Compound (D-974))

Under argon flow, add 3.8 g (10 mmol) of 6,12-dibromo , 3.4g (25mmol) of N-isopropylaniline, 0.03g (1.5% mole) of palladium acetate, 0.06g (3% mole) of tri-tert-butylphosphine, 2.4g (25mmol) of sodium tert-butoxide and 100 mL of dry toluene, and the resulting solution was stirred overnight under heating at 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 2.0 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (D-974) (yield: 40%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used to measure, and the results of the ¹ H-NMR spectrum of the obtained compound (D-974) are shown in FIG. 10 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of the compound (D-974) in toluene solvent were 362 nm and 436 nm, respectively.

[0165]

Synthesis Example 11 (Synthesis of Compound (D-998))

Under argon flow, add 3.8 g (10 mmol) of 6,12-dibromo , 5.3g (25mmol) of N-(4-isopropylphenyl) pyridin-3-amine, O.03g (1.5% mole) of palladium acetate, O.06g (3-tert-butyl phosphine) , 2.4 g (25 mmol) of sodium tert-butoxide and 100 mL of dry toluene, and the resulting solution was stirred overnight under heating at a temperature of 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 4.2 g of white powder. According to FD-MS measurement, the obtained product was identified as compound (D-998) (yield: 65%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used to measure the results of the ¹ H-NMR spectrum of the obtained compound (D-998) shown in FIG. 11 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of compound (D-998) in toluene solvent were 393nm and 444nm, respectively.

[0166]

Synthesis Example 12 (Synthesis of Compound (D-1000))

、5.3g(25mmol)的N-(4-异丙基苯基)吡啶-3-胺、O.03g(1.5％摩尔)的乙酸钯、O.06g(30％摩尔)的三叔丁基膦、2.4g(25mmol)的叔丁醇钠和100mL干燥的甲苯，在100℃温度加热下，将得到的溶液搅拌一夜。反应终止后，过滤分离沉淀的晶体，用50mL甲苯和100mL甲醇洗涤，得到5.3g浅黄色粉末。根据FD-MS测定，确定得到的产物为化合物(D-1000)(收率：80％)。Under argon flow, add 3.9 g (10 mmol) of 2-methyl-6,12-dibromo to a 300 mL three-necked flask equipped with a condenser

, 5.3g (25mmol) of N-(4-isopropylphenyl) pyridin-3-amine, 0.03g (1.5% mole) of palladium acetate, 0.06g (30% mole) of tri-tert-butylphosphine , 2.4 g (25 mmol) of sodium tert-butoxide and 100 mL of dry toluene, and the resulting solution was stirred overnight under heating at a temperature of 100°C. After the reaction was terminated, the precipitated crystals were separated by filtration and washed with 50 mL of toluene and 100 mL of methanol to obtain 5.3 g of light yellow powder. According to FD-MS measurement, the obtained product was identified as compound (D-1000) (yield: 80%).

Using dichloromethane as a solvent, DRX-500 (trade name: manufactured by Brucker Optics Inc) was used for measurement, and the result of ¹ H-NMR spectrum of the obtained compound (D-1000) is shown in FIG. 12 . In addition, the maximum absorption wavelength and maximum fluorescence wavelength of the compound (D-1000) in toluene solvent were 385 nm and 440 nm, respectively.

[0167]

Example 1

A 120 nm thick transparent electrode made of indium oxide was formed on a glass substrate of 25 mm x 75 mm x 1.1 mm. The glass substrate with the transparent electrode was cleaned with ultraviolet irradiation and ozone. The cleaned glass substrate with transparent electrodes was then fixed in a vacuum vapor deposition apparatus.

First, N',N"-bis[4-(diphenylamino)phenyl]-N',N"-diphenylbiphenyl-4,4'-diamine was vapor-deposited to form a 60nm-thick The hole injection layer, and then vapor-deposit N, N, N', N'-tetrakis(4-biphenyl)-4,4'-bendizine on the hole injection layer to form a hole with a thickness of 20nm transport layer. Then, on the hole transport layer, 10,10'-bis[1,1',4',1"]terphenyl-2-yl-9,9' was simultaneously vapor-deposited in a weight ratio of 40:2 - Bianthracenyl and the above compound (9) to form a light emitting layer having a thickness of 40 nm.

Then, tris(8-quinolinolate)aluminum was vapor-deposited on the light emitting layer to form an electron injection layer having a thickness of 10 nm. On this electron injection layer, tris(8-quinolinephenolate)aluminum and lithium were vapor-deposited at a weight ratio of 10:0.3 to form a layer with a thickness of 10 nm, and aluminum was further vapor-deposited thereon to form a layer with a thickness of 150 nm. aluminum layer. This aluminum layer functions as a cathode. Thus, an organic EL device was fabricated.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 602 cd/m ² (peak wavelength of light emission: 464 nm) and the current efficiency was 6.0 cd/m 2 at a voltage of 6.0 V and a current density of 10 mA/cm ² . A Blu-ray. Sustainability testing of the device by passing a DC current at an initial luminance of 500 cd/ ^m2 demonstrated a half-life of 18900 hours.

[0168]

Example 2

According to the same method as in Example 1, but substituting compound (9) with compound (23), an organic EL device was prepared.

The thus-obtained organic EL device was detected through a current, and it was confirmed that at a voltage of 6.5 V and a current density of 10 mA/cm ² , the emission luminance was 664 cd/m ² (peak wavelength of light emission: 462 nm) and the current efficiency was 6.6 cd/m 2 . A Blu-ray. Sustainability testing of the device by passing a DC current at an initial luminance of 500 cd/ ^m2 demonstrated a half-life of 16,000 hours.

[0169]

Example 3

The same procedure was carried out according to Example 1, but substituting 10-(3-(naphthalen-1-yl)phenyl)-9-(naphthalen-2-yl)anthracene for 10,10'-bis[1,1' , 4', 1"] terphenyl-2-yl-9,9'-bianthracene to make an organic EL device.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 631cd/ ^m2 (peak wavelength of light emission: 464nm) and the current efficiency was 6.3cd/m2 at a voltage of 6.5V and a current density of 10mA/ ^cm2 . A Blu-ray. The device was continuously tested by starting to pass a DC current at an initial luminance of 500 cd/m ² , and it was confirmed that its half-life was 20,000 hours or more.

[0170]

Example 4

According to the same method as in Example 3, but using compound (23) instead of compound (9) as a dopant substance, an organic EL device was fabricated.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 710 cd/m ² (peak wavelength of light emission: 465 nm) and the current efficiency was 7.1 cd/m 2 at a voltage of 6.5 V and a current density of 10 mA/cm ² . A Blu-ray. The device was continuously tested by starting to pass a DC current at an initial luminance of 500 cd/m ² , and it was confirmed that its half-life was 20,000 hours or more.

[0171]

Example 5

According to the same method as in Example 3, but using compound (25) instead of compound (9) as a dopant substance, an organic EL device was fabricated.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 793 cd/m ² (peak wavelength of light emission: 469 nm) and the current efficiency was 7.9 cd/m 2 at a voltage of 6.5 V and a current density of 10 mA/cm ² . A Blu-ray. The device was continuously tested by starting to pass a DC current at an initial luminance of 500 cd/m ² , and it was confirmed that its half-life was 20,000 hours or more.

[0172]

Example 6

According to the same method as in Example 3, but using compound (10) instead of compound (9) as a dopant substance, an organic EL device was fabricated.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 782 cd/m ² (peak wavelength of light emission: 468 nm) and the current efficiency was 7.8 cd/m 2 at a voltage of 6.5 V and a current density of 10 mA/cm ² . A Blu-ray. The device was continuously tested by starting to pass a DC current at an initial luminance of 500 cd/m ² , and it was confirmed that its half-life was 20,000 hours or more.

[0173]

Comparative Example 1

The same method carried out according to Example 1, but with 6,12-bis(4-isopropylphenyl-p-tolylamino) Instead of compound (9), an organic EL device was fabricated.

The thus-obtained organic EL device was detected through a current, and it was confirmed that the emission luminance was 594 cd/m ² (peak wavelength of light emission: 462 nm) and the current efficiency was 5.9 cd/m 2 at a voltage of 6.3 V and a current density of 10 mA/cm ² . A Blu-ray. Sustainability testing of the device by passing a DC current starting at an initial luminance of 500 cd/ ^m2 demonstrated a half-life of 4590 hours.

骨架结构结合时，由于各化舍物之间彼此结合，半寿期缩短。It is obvious from the above results that when any substituent is not combined with diamino

When the skeleton structure is combined, the half-life is shortened due to the combination of various chemicals.

industrial application

[0174]

The organic EL device using the arylamine derivative of the present invention exhibits practically sufficient luminance even at a very low voltage, and has increased luminous efficiency, and the device does not exhibit a property of deterioration after a long period of use, so It has the characteristics of long service life. Therefore, the EL device can be used as a flat-panel light-emitting element of a wall-mounted television or as a light source for a backlight of a display.

Claims (11)

1. An arylamine derivative represented by the following general formula (1):

Wherein A ₁ to A ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group with 1-50 carbon atoms, a substituted or unsubstituted aryl group with 5-50 ring carbon atoms, a 6- Substituted or unsubstituted aralkyl with 50 ring carbon atoms, substituted or unsubstituted cycloalkyl with 3-50 ring carbon atoms, substituted or unsubstituted with 1-50 ring carbon atoms Alkoxy, substituted or unsubstituted aryloxy with 5-50 ring carbon atoms, substituted or unsubstituted arylamino with 5-50 ring carbon atoms, substituted with 1-20 carbon atoms or unsubstituted alkylamino, substituted or unsubstituted heterocyclyl having 3-50 ring carbon atoms, substituted or unsubstituted silyl or halogen atoms having 3-50 carbon atoms; a, b, c and d each independently represent an integer of 0-5, when a, b, c or d are each an integer of 2 or more, _A1 to _A4 can be the same or different from each other, and can be combined with each other to form A saturated or unsaturated ring; and in addition, a pair of _A1 and _A2 and a pair of _A3 and _A4 can be combined with each other to form a saturated or unsaturated ring; R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms, a substituted or unsubstituted aryl group having 6-50 substituted or unsubstituted aralkyl with 3 ring carbon atoms, substituted or unsubstituted cycloalkyl with 3-50 ring carbon atoms, substituted or unsubstituted aryl with 5-20 ring carbon atoms Amino, substituted or unsubstituted alkylamino with 1-20 carbon atoms, substituted or unsubstituted heterocyclic group with 3-50 ring carbon atoms or substituted or unsubstituted with 3-50 carbon atoms Unsubstituted silyl groups; a pair of R ₁ and R ₂ and a pair of R ₃ and R ₄ can be combined with each other to form a saturated or unsaturated ring; However, the case where all R ₁ to R ₄ are hydrogen atoms in the general formula (1) is excluded. 2. The arylamine derivative according to claim 1, wherein in the general formula (1) R ₁ or R ₃ at least one independently represents a substituted or unsubstituted alkyl group with 1-50 carbon atoms, with 5-50 A substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted cycloalkane having 3 to 50 ring carbon atoms base. 3. The arylamine derivative according to claim 1, wherein in the general formula ( ₁ ), R and R _each independently represent a substituted or unsubstituted alkyl group with 1-50 carbon atoms, with 5-50 rings A substituted or unsubstituted aryl group of carbon atoms, a substituted or unsubstituted aralkyl group having 6-50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3-50 ring carbon atoms. 4. according to the arylamine derivative of claim 1, wherein in the general formula (1) at least one of _R2 or _R4 independently represents a substituted or unsubstituted primary alkyl group with 1-50 carbon atoms, with 1- Substituted or unsubstituted secondary alkyl with 50 carbon atoms, substituted or unsubstituted aryl with 5-50 ring carbon atoms, substituted or unsubstituted arane with 1-50 ring carbon atoms A group or a substituted or unsubstituted cycloalkyl group having 3-50 ring carbon atoms. 5. The arylamine derivative according to claim 1, wherein in the general formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted arylamino group with 5-20 ring carbon atoms, having A substituted or unsubstituted alkylamino group having 1-20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3-50 ring carbon atoms, or a substituted or unsubstituted group having 3-50 carbon atoms Silyl. 6. An arylamine derivative represented by the following general formula (2): Wherein A ₅ to A ₈ each independently represent a substituted or unsubstituted alkyl group with 1-50 carbon atoms, a substituted or unsubstituted aryl group with 5-50 ring carbon atoms, a substituted or unsubstituted aryl group with 3-50 ring A substituted or unsubstituted cycloalkyl group of carbon atoms or a substituted or unsubstituted heterocyclic group having 3-50 ring carbon atoms; R ₅ to R ₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted aryl group having 5-50 ring carbon atoms, a substituted or unsubstituted aryl group having 6-50 substituted or unsubstituted aralkyl with 3 ring carbon atoms, substituted or unsubstituted cycloalkyl with 3-50 ring carbon atoms, substituted or unsubstituted aryl with 5-20 ring carbon atoms Amino, substituted or unsubstituted alkylamino with 1-20 carbon atoms or substituted or unsubstituted heterocyclic group with 3-50 ring carbon atoms; and a pair of R ₅ and R ₆ and a pair of R ₇ and R ₈ may combine with each other to form a saturated or unsaturated ring. 7. The arylamine derivative according to any one of claims 1 to 6, which is a dopant substance for an organic electroluminescence device. 8. An organic electroluminescent device comprising at least one organic thin film layer comprising a light emitting layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein at least one of said organic thin film layers comprises a single Arylamine derivatives or mixture components thereof according to any one of claims 1-6. 9. The organic electroluminescent device according to claim 8, wherein said light emitting layer comprises the arylamine derivative according to any one of claims 1 to 6 alone or a mixture component thereof. 10. The organic electroluminescent device according to claim 8, wherein the light emitting layer contains the arylamine derivative according to any one of claims 1 to 6 in an amount of 0.1 to 20% by weight. 11. The organic electroluminescent device according to claim 8, which emits blue light.

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