CN1980884A

CN1980884A - Aromatic amine derivative and organic electroluminescent device using the same

Info

Publication number: CN1980884A
Application number: CN 200580021297
Authority: CN
Inventors: 舟桥正和
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2004-08-31
Filing date: 2005-08-26
Publication date: 2007-06-13

Abstract

The invention discloses an arylamine derivative with a special structure of * structure. Also disclosed is an organic electroluminescent device wherein the 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 an aromatic amine derivative by itself or a mixture component thereof. Such an organic electroluminescent device has a long life span and high luminous efficiency, and emits blue light having high color purity. The aromatic amine derivative enables the realization of such an organic electroluminescent device.

Description

Aryl amine derivatives and use the Organnic electroluminescent device of this derivative

Technical field

[0001]

A kind of Organnic electroluminescent device (organic electroluminescence device) that the present invention relates to a kind of aryl amine derivatives and use this derivative, more particularly, relate to a kind of Organnic electroluminescent device with long life (long lifetime), efficient luminous and emission high purity blue light; And relate to the aryl amine derivatives that to realize this Organnic electroluminescent device.

Background of invention

[0002]

Expectation at present will utilize organic electroluminescent (following sometimes " electroluminescent " is referred to as " the EL ") device of organic substance to be used as a kind of inexpensive full color indicating meter with large-sized solid luminescence type, about the various researchs of organic El device in progress.Organic El device has usually and comprises light-emitting layer and a pair of structure that clips the electrode of this light-emitting layer.The light emission of organic El device is a kind of phenomenon, wherein when adding an electric field between the two poles of the earth, electronics injects from negative electrode one side, and injects the electron hole from anode one side, combine formation excited state with the hole at this electronics of emission layer, the energy that produces when excited state goes back to ground state is emitted as light.

Compare with inorganic light-emitting diode, conventional organic El device needs high driving voltage and only presents the light emission of low-light level or poor efficiency.In addition, the degradation characteristic of conventional organic El device is very waste also, therefore, does not in fact use.Though organic El device progressively develops in recent years, still require to develop to have higher light emission efficient and organic El device with long life.

For example, a kind of technology (with reference to following patent documentation 1) of using single single anthracene compound as organic luminescent substance is now disclosed.But in this technology, the low lightness that adopts this material acquisition is to 1650cd/m ², for example, current density is 165mA/cm ², its light emission efficient is also very low, only is 1cd/A promptly, and in fact this value can not be used.A kind of technology (with reference to following patent documentation 2) of using single two anthracene compounds as organic luminescent substance is also disclosed at present.But in this technology, the luminous efficiency that adopts this material to obtain also is low to moderate about 1-3cd/A.Therefore, show a kind of improved technology of demand so that it can be used actually.In addition, a kind of technology (with reference to following patent documentation 3) of using toluylene based compound and adding styrylamine etc. as organic luminescent substance is now also disclosed.But its disclosed device can not demonstrate the sufficiently long life-span, therefore, still needs and further improves.

In addition, now disclose a kind of use single-or two anthracene compounds and toluylene based compound as the technology (with reference to following patent documentation 4) in organic light emission middle layer.But in these technology, the wavelength that the structure that the distyryl compound yoke closes has extended emmission spectrum has destroyed colour purity.

In addition, following patent documentation 5 discloses the use diamino

(chrysene) the emission blue-ray devices of derivative.But, although on light emission efficient, have superiority since this device lifetime deficiency, also need further to improve.

[0003]

Patent documentation 1: Japanese unexamined patent

Te Kaidi Hei 11-3782A number

Patent documentation 2: Japanese unexamined patent

No. 8 (1996)-012600, Te Kaidi Hei

Patent documentation 3: the open PCT WO00/06402 of international patent application

Patent documentation 4: Japanese unexamined patent

Te Kaidi 2001-284050 number

Patent documentation 5: the open PCT WO04/04088 of international application

Disclosure of the Invention

[0004]

The present invention has overcome the problems referred to above.The purpose of this invention is to provide and have the long life and efficient luminiferous organic El device, and the aryl amine derivatives that can realize this organic El device.

[0005]

The broad research result who has the aryl amine derivatives of above-mentioned suitable character and use the organic El device of described aryl amine derivatives as development, it has been observed by the present inventors that target of the present invention can realize by using by the aryl amine derivatives of following general formula (1) or (2) representative, wherein said amino and replacement

The structure combination.On the basis of above-mentioned discovery, realized the present invention.

[0006]

That is, the invention provides a kind of aryl amine derivatives by following general formula (1) or general formula (2) representative:

[0007]

In general formula (1), A ₁To A ₄The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 1-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted alkoxyl group with 1-50 carbon atom, replacement or unsubstituted aryloxy with 5-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-50 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 3-50 ring carbon atom replacement or unsubstituted heterocyclic, have 3-50 carbon atom replacement or unsubstituted silyl or halogen atom.

A, b, c and d independently represent the integer of 0-5 separately, when a, b, c or d respectively do for oneself integer more than 2 or 2, and A ₁To A ₄Can be same to each other or different to each other, and the saturated or undersaturated ring of formation that can be bonded to each other; And a pair of A in addition, ₁And A ₂And a pair of A ₃And A ₄Can be bonded to each other and form saturated or undersaturated ring;

R ₁To R ₄The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 6-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-20 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 3-50 ring carbon atom replacement or unsubstituted heterocyclic or have replacement or the unsubstituted silyl of 3-50 carbon atom; A pair of R ₁And R ₂And a pair of R ₃And R ₄Can be bonded to each other and form saturated or undersaturated ring;

But, get rid of all R in the general formula (1) ₁To R ₄It all is the situation of hydrogen atom.

[0008]

In general formula (2), A ₅To A ₈Independent separately representative have 1-50 carbon atom replacement or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 3-50 ring carbon atom replacement or unsubstituted cycloalkyl or have 3-50 ring carbon atom replacement or unsubstituted heterocyclic;

R ₅To R ₈The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 6-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-20 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino or have 3-50 ring carbon atom replacement or unsubstituted heterocyclic; And a pair of R ₅And R ₆And a pair of R ₇And R ₈Can be bonded to each other and form saturated or undersaturated ring.

[0009]

In addition, the invention provides a kind of organic El device, it comprises at least a organic thin film layer, and this thin film layer comprises a light-emitting layer that is clipped between the electrode pair that anode and negative electrode form, and wherein at least a described organic thin film layer comprises single described aryl amine derivatives or its mix ingredients.

[0010]

Use the described organic El device of aryl amine derivatives of the present invention even under very low applied voltage, also demonstrate brightness enough in the practicality, present the luminous efficiency of increase, and the deterioration after the long-time use presented resistance, thereby demonstrate the work-ing life of its prolongation.

The diagram summary

[0011]

Fig. 1 is that to be presented at the compound (4) that obtains among the synthetic embodiment 1 relevant ¹H-NMR measurement result figure;

Fig. 2 is that to be presented at the compound (9) that obtains among the synthetic embodiment 2 relevant ¹H-NMR measurement result figure;

Fig. 3 is that to be presented at the compound (20) that obtains among the synthetic embodiment 3 relevant ¹H-NMR measurement result figure;

Fig. 4 is that to be presented at the compound (23) that obtains among the synthetic embodiment 4 relevant ¹H-NMR measurement result figure;

Fig. 5 is that to be presented at the compound (25) that obtains among the synthetic embodiment 5 relevant ¹H-NMR measurement result figure;

Fig. 6 is that to be presented at the compound (39) that obtains among the synthetic embodiment 6 relevant ¹H-NMR measurement result figure;

Fig. 7 is that to be presented at the compound (57) that obtains among the synthetic embodiment 7 relevant ¹H-NMR measurement result figure;

Fig. 8 is that to be presented at the compound (95) that obtains among the synthetic embodiment 8 relevant ¹H-NMR measurement result figure;

Fig. 9 is that to be presented at the compound (D-973) that obtains among the synthetic embodiment 9 relevant ¹H-NMR measurement result figure;

Figure 10 is that to be presented at the compound (D-974) that obtains among the synthetic embodiment 10 relevant ¹H-NMR measurement result figure;

Figure 11 is that to be presented at the compound (D-998) that obtains among the synthetic embodiment 11 relevant ¹H-NMR measurement result figure; With

Figure 12 is that to be presented at the compound (D-1000) that obtains among the synthetic embodiment 12 relevant ¹H-MR measurement result figure.

Implement the preferred embodiments of the invention

[0012]

The invention provides a kind of aryl amine derivatives by following general formula (1) or general formula (2) representative:

At first, below will explain aryl amine derivatives by general formula (1) representative.

[0013]

In general formula (1), A ₁To A ₄The independent separately hydrogen atom of representing, have the individual carbon atom of 1-50 (preferred 1-20) replacement or unsubstituted alkyl, replacement or unsubstituted aryl with the individual ring carbon atom of 5-50 (preferred 5-20), replacement or unsubstituted aralkyl with the individual ring carbon atom of 1-50 (preferred 6-20), replacement or unsubstituted cycloalkyl with the individual ring carbon atom of 3-50 (preferred 5-12), replacement or unsubstituted alkoxyl group with the individual carbon atom of 1-50 (preferred 1-6), replacement or unsubstituted aryloxy with the individual ring carbon atom of 5-50 (preferred 5-18), replacement or unsubstituted virtue amino with the individual ring carbon atom of 5-50 (preferred 5-18), have the individual carbon atom of 1-20 (preferred 1-6) replacement or unsubstituted alkyl amino, have the individual ring carbon atom of 3-50 (preferred 3-20) replacement or unsubstituted heterocyclic, have the individual carbon atom of 3-50 (preferred 3-20) replacement or unsubstituted silyl or halogen atom.

[0014]

A ₁To A ₄Example replacement or unsubstituted alkyl of representative comprises methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, octadecyl, trichloromethyl, trifluoromethyl etc.

A ₁To A ₄Example replacement or unsubstituted aryl of representative comprises phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, xenyl, 4-methyl biphenyl, 4-ethyl biphenyl base, 4-cyclohexyl biphenyl base, terphenyl, 3,5-dichlorophenyl, naphthyl, 5-methyl naphthyl, anthryl, pyrenyl etc.

[0015]

A ₁To A ₄Example replacement or unsubstituted aralkyl of representative comprises benzyl, α, the Alpha-Methyl phenylbenzyl, trityl group, the 1-styroyl, the 2-styroyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, the phenyl tertiary butyl,-menaphthyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl sec.-propyl,-Alpha-Naphthyl sec.-propyl, β-menaphthyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl sec.-propyl, 2-betanaphthyl sec.-propyl, α-phenoxy benzyl, α-benzyloxy benzyl, α, α-bis trifluoromethyl benzyl, 1-pyrryl methyl, 2-(1-pyrryl) ethyl, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, to hydroxybenzyl, between hydroxybenzyl, adjacent hydroxybenzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-hydroxyl-2-propyloxy phenyl base and 1-chloro-2-propyloxy phenyl base etc.

[0016]

A ₁To A ₄The example of the cycloalkyl of representative comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.

A ₁To A ₄The example of the alkoxyl group of representative comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, various pentyloxy, various hexyloxy etc.

A ₁To A ₄The example of the aryloxy of representative comprises phenoxy group, tolyloxy, naphthyloxy etc.

A ₁To A ₄The example of the arylamino of table comprises diphenyl amino, xylyl amino, isopropyl diphenyl base amino, tert-butyl diphenyl amino, di-isopropyl diphenyl amino, di-t-butyl diphenyl amino, dinaphthyl amino, naphthyl phenyl amino etc.

A ₁To A ₄The example of the alkylamino of representative comprises dimethylamino, diethylamino, dihexyl amino etc.

A ₁To A ₄The example of the heterocyclic radical of representative comprises the group of imidazoles, benzoglyoxaline, pyrroles, furans, thiophene, thionaphthene,  bisoxazoline (oxadiazoline), indoline, carbazole, pyridine, quinoline, isoquinoline 99.9, benzoquinones, pyrazoline, imidazolidine, piperidines etc.

A ₁To A ₄Example replacement or unsubstituted silyl of representative comprises trimethyl silyl, triethylsilyl, t-butyldimethylsilyl, vinyl-dimethyl base silyl, propyl-dimethyl silyl, methyldiphenyl base silyl, 3,5-dimethylphenyl silyl, triphenyl silyl etc.

A ₁To A ₄The example of the halogen atom of representative comprises fluorine atom, chlorine atom, bromine atoms etc.

[0017]

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

When a, b, c or d respectively do for oneself integer more than 2 or 2, A ₁To A ₄Can be same to each other or different to each other, and the saturated or undersaturated ring of formation that can be bonded to each other; And a pair of A in addition, ₁And A ₂And a pair of A ₃And A ₄Can be bonded to each other and form saturated or undersaturated ring;

The example of described ring comprises the naphthenic hydrocarbon with 4-12 carbon atom, as tetramethylene, pentamethylene, hexanaphthene, diamantane, norbornane etc.; Cycloolefin with 4-12 carbon atom is as cyclobutene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene etc.; Cyclodiene (cycloalkadierie) with 6-12 carbon atom is as cyclohexadiene, cycloheptadiene, cyclooctadiene etc.; Aromatic ring with 6-50 carbon atom, as benzene, naphthalene, phenanthrene, anthracene, pyrene,

, acenaphthene etc.

[0018]

In general formula (1), R ₁To R ₄The independent separately hydrogen atom of representing, have the individual carbon atom of 1-50 (preferred 1-20) replacement or unsubstituted alkyl (preferred primary alkyl or secondary alkyl), replacement or unsubstituted aryl with the individual ring carbon atom of 5-50 (preferred 5-20), replacement or unsubstituted aralkyl with the individual ring carbon atom of 6-50 (preferred 6-20), replacement or unsubstituted cycloalkyl with the individual ring carbon atom of 3-50 (preferred 5-12), replacement or unsubstituted virtue amino with the individual ring carbon atom of 5-20 (preferred 5-18), have the individual carbon atom of 1-20 (preferred 1-10) replacement or unsubstituted alkyl amino, have the individual ring carbon atom of 3-50 (preferred 3-20) replacement or unsubstituted heterocyclic or have replacement or the unsubstituted silyl of the individual carbon atom of 3-50 (preferred 3-20); A pair of R ₁And R ₂And a pair of R ₃And R ₄Can be bonded to each other and form saturated or undersaturated ring.

R ₁To R ₄Specific examples and above the A replacement of representative or unsubstituted alkyl, aryl, aralkyl, cycloalkyl, virtue amino, alkylamino, heterocyclic radical, silyl and saturated or undersaturated ring ₁To A ₄Those examples of enumerating are identical.

Preferred especially R ₂And R ₄The alkyl of representative is primary alkyl or secondary alkyl.

[0019]

In addition, A ₁To A ₄And R ₁To R ₄The substituting group example comprise and have 5-50 replacement or the unsubstituted aryl of (preferred 5-20) individual ring carbon atom, have the individual carbon atom of 1-50 (preferred 1-20) replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group with the individual carbon atom of 1-50 (preferred 1-20), replacement or unsubstituted aralkyl with the individual ring carbon atom of 6-50 (preferred 6-20), replacement or unsubstituted aryloxy with the individual ring carbon atom of 5-50 (preferred 5-20), replacement or unsubstituted arylthio with the individual ring carbon atom of 5-50 (preferred 5-20), replacement or unsubstituted alkoxy carbonyl with the individual carbon atom of 1-50 (preferred 1-20), amino, halogen atom, cyano group, nitro, hydroxyl, carboxyl etc.

[0020]

But, get rid of all R in the general formula (1) ₁To A ₄It all is the situation of hydrogen atom.

In addition, in general formula (1), preferred R ₁And/or R ₃Independent representative have 1-50 carbon atom replacement or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 6-50 ring carbon atom replacement or unsubstituted aralkyl or have replacement or the unsubstituted cycloalkyl of 3-50 ring carbon atom.Preferred R ₁And R ₃Independent separately representative have 1-50 carbon atom replacement or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 6-50 ring carbon atom replacement or unsubstituted aralkyl or have replacement or the unsubstituted cycloalkyl of 3-50 ring carbon atom.

In addition, in general formula (1), also preferred R ₁To R ₄Independently separately represent hydrogen atom, have 5-20 ring carbon atom replacement or unsubstituted arylamino, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 5-50 ring carbon atom replacement or unsubstituted heterocyclic or have replacement or the unsubstituted silyl of 3-50 carbon atom.

In addition, preferred R ₁And/or R ₃Represent methylidene, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl or cyclohexyl.

In addition, preferred R ₂And/or R ₄Represent methylidene, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl or cyclohexyl.

[0021]

Secondly, below will explain the aryl amine derivatives of representing by general formula (2):

[0022]

In general formula (2), A ₅To A ₈Independent separately representative have the individual carbon atom of 1-50 (preferred 1-20) replacement or unsubstituted alkyl, have the individual ring carbon atom of 5-50 (preferred 5-20) replacement or unsubstituted aryl, have the individual ring carbon atom of 3-50 (preferred 5-12) replacement or unsubstituted cycloalkyl or have the individual ring carbon atom of 3-50 (preferred 3-20) replacement or unsubstituted heterocyclic;

In general formula (2), R ₅To R ₈The independent separately hydrogen atom of representing, have the individual carbon atom of 1-50 (preferred 1-20) replacement or unsubstituted alkyl, replacement or unsubstituted aryl with the individual ring carbon atom of 5-50 (preferred 5-20), replacement or unsubstituted aralkyl with the individual ring carbon atom of 6-50 (preferred 6-20), replacement or unsubstituted cycloalkyl with the individual ring carbon atom of 3-50 (preferred 5-12), replacement or unsubstituted virtue amino with the individual ring carbon atom of 5-20 (preferred 5-12), have the individual carbon atom of 1-20 (preferred 1-10) replacement or unsubstituted alkyl amino or have the individual ring carbon atom of 3-50 (preferred 3-20) replacement or unsubstituted heterocyclic; A pair of R ₅And R ₆And a pair of R ₇And R ₈Can be bonded to each other and form saturated or undersaturated ring.

In the general formula (2) by A ₅To A ₈And R ₅To R ₈The specific examples of the group of representative, those substituent specific exampless and those specific examples and the middle A of above general formula (1) saturated or undersaturated ring ₁To A ₄And R ₁To R ₄Those cited examples are identical.

Specific examples by the aryl amine derivatives of general formula (1) or general formula (2) representative will illustrate following, but specifically not be confined to this.Simultaneously, in following compounds, the Me represent methylidene.

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] [table 1]

[0037] [table 2]

[0038] [table 3]

[0039] [table 4]

[0040] [table 5]

[0041] [table 6]

[0042] [table 7]

[0043] [table 8]

[0044] [table 9]

[0045] [table 10]

[0046] [table 11]

[0047] [table 12]

[0048] [table 13]

[0049] [table 14]

[0050] [table 15]

[0051] [table 16]

[0052] [table 17]

[0053] [table 18]

[0054] [table 19]

[0055] [table 20]

[0056] [table 21]

[0057] [table 22]

[0058] [table 23]

[0059] [table 24]

[0060] [table 25]

[0061] [table 26]

[0062] [table 27]

[0063] [table 28]

[0064] [table 29]

[0065] [table 30]

[0066] [table 31]

[0067] [table 32]

[0068] [table 33]

[0069] [table 34]

[0070] [table 35]

[0071] [table 36]

[0072] [table 37]

[0073] [table 38]

[0074] [table 39]

[0075] [table 40]

[0076] [table 41]

[0077] [table 42]

[0078] [table 43]

[0079] [table 44]

[0080] [table 45]

[0081] [table 46]

[0082] [table 47]

[0083] [table 48]

[0084] [table 49]

[0085] [table 50]

[0086] [table 51]

[0087] [table 52]

[0088] [table 53]

[0089] [table 54]

[0090] [table 55]

[0091] [table 56]

[0092] [table 57]

[0093] [table 58]

[0094] [table 59]

[0095] [table 60]

[0096] [table 61]

[0097] [table 62]

[0098] [table 63]

[0099] [table 64]

[0100] [table 65]

[0101] [table 66]

[0102] [table 67]

[0103] [table 68]

[0104] [table 69]

[0105] [table 70]

[0106] [table 71]

[0107] [table 72]

[0108] [table 73]

[0109] [table 74]

[0110] [table 75]

[0111] [table 76]

[0112] [table 77]

[0113] [table 78]

[0114] [table 79]

[0115] [table 80]

[0116] [table 81]

[0117] [table 82]

[0118] [table 83]

[0119] [table 84]

[0120] [table 85]

[0121] [table 86]

[0122] [table 87]

[0123] [table 88]

[0124] [table 89]

[0125]

In aryl amine derivatives of the present invention, because aryl (especially phenyl ring), alkyl, cycloalkyl or heterocyclic radical are connected with diamino sugarcane structure as luminescence center, stoped the association (association) between the compound, cause its prolongation in work-ing life.In addition, since the substituting group of large volume with The coupling of skeleton structure has increased the steric repulsion to described amine structure, has therefore also further prolonged its work-ing life.

In addition, described aryl amine derivatives has strong fluorescence in solid-state, and is very outstanding in the electric field light emission, can make fluorescence quantum efficiency up to O.3 or O.3.In addition, aryl amine derivatives of the present invention not only presents the good injection from metal electrode or organic thin film layer or the ability of transporting holes, also present the good injection from metal electrode or organic thin film layer or the ability of transmission electronic, therefore, usually can be used as the light emission material, in particular for the dopant (doping materials) of organic El device.In addition, aryl amine derivatives of the present invention can use with other hole transport (hole transporting) material, electric transmission material or dopant.

[0126]

Organic El device of the present invention comprises one or more organic thin film layers that are clipped between anode and the negative electrode.Under the situation of one deck type, be sandwiched between anode and the negative electrode as the light-emitting layer of organic thin film layer.This light-emitting layer comprises described luminophore, and also can comprise in order to be delivered to hole injected material and electronics injected material on the described luminophore from the anode injected holes or from the negative electrode injected electrons.Aryl amine derivatives of the present invention has the photoemissive character of enhancing and good hole injection properties and hole transport characteristic, also has good Electron Injection Characteristics and electron transport property, therefore, can be used as luminophore and dopant in the light-emitting layer.

In organic El device of the present invention, O.1-20% the weight ratio that described light-emitting layer comprises aryl amine derivatives of the present invention is preferably, more preferably 1-10% weight.In addition, aryl amine derivatives of the present invention not only presents very high fluorescence quantum efficiency, also present high cavity transmission ability and electron transport ability, and have the ability that forms uniform thin film, therefore can only form described light-emitting layer by described aryl amine derivatives.

On the other hand, when organic El device of the present invention comprises when having at least one two or more organic thin film layer that are clipped in the light-emitting layer between anode and the negative electrode, this organic thin film layer preferably includes the organic layer that contains as the aryl amine derivatives of the present invention of main component, and this organic layer is between anode and the light-emitting layer.This organic layer can be hole injection layer, hole transmission layer etc.

[0127]

In addition, when aryl amine derivatives of the present invention when the dopant, the pyrene derivatives that preferably uses at least a anthracene derivant that is selected from the anthracene derivant of following general formula (3), following general formula (4) and following general formula (5) is as essential substance (host material).

[0128]

In general formula (3), X ₁And X ₂The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 6-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted alkoxyl group with 1-50 ring carbon atom, replacement or unsubstituted aryloxy with 5-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-50 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 5-50 ring carbon atom replacement or unsubstituted heterocyclic or halogen atom; E or f independently represent the integer of 0-4 separately; When e or f are integer more than 2 or 2, X ₁To X ₂Can be same to each other or different to each other.

Ar ₁And Ar ₂Independent separately representative have 5-50 ring carbon atom replacement unsubstituted aryl or have 5-50 ring carbon atom replacement or unsubstituted heterocyclic; Ar ₁Or Ar ₂At least one representative has fused rings and has replacement or the unsubstituted aryl of 10-50 ring carbon atom; M represents the integer of 1-3.When m was integer more than 2 or 2, the group in the above bracket [] can be same to each other or different to each other.

X ₁, X ₂, Ar ₁And Ar ₂Concrete example and substituting group and above general formula (1) in those of explanation identical.

[0129]

[0130]

In general formula (4), X ₁To X ₃The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 6-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted alkoxyl group with 1-50 carbon atom, replacement or unsubstituted aryloxy with 5-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-50 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 5-50 ring carbon atom replacement or unsubstituted heterocyclic or halogen atom; E, f and g independently represent the integer of 0-4 separately.When e, f or g are integer more than 2 or 2, X ₁, X ₂And X ₃Can be same to each other or different to each other.

Ar ₁Representative has fused rings and has replacement or the unsubstituted aryl of 10-50 ring carbon atom, Ar ₃Represent replacement or the unsubstituted aryl of a tool 5-50 ring carbon atom; N represents the integer of 1-3.When n was integer more than 2 or 2, the group in the above bracket [] can be same to each other or different to each other.

X ₁To X ₃, Ar ₁And Ar ₃Concrete example and substituting group and above general formula (1) in those of explanation identical.

[0131]

Below illustrate the specific examples of the anthracene derivant of general formula (3) and (4) representative, but be not confined to this especially.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

In general formula (5), Ar ₅And Ar ₆Representative has replacement or the unsubstituted aryl of 6-50 ring carbon atom separately;

L ₁And L ₂That independent separately representative replaces or unsubstituted phenylene, replacement or unsubstituted naphthylidene, dibenzo silolylene base replacement or unsubstituted fluorenylidene or replacement or unsubstituted;

S represents the integer of 0-2, and p represents the integer of 1-4, and q represents the integer of 0-2, and r represents the integer of 0-4; And

L ₁Or Ar ₅Be connected in any position of the 1-5 position of pyrene, and L ₂And Ar ₆Be connected with any position of its 6-10 position,

But, when p+r is even number, Ar ₅, Ar ₆, L ₁And L ₂Satisfy following prerequisite (1) or prerequisite (2):

(1) Ar ₅≠ Ar ₆And/or L ₁≠ L ₂(wherein ≠ refer to that each group has different structures)

(2) work as Ar ₅=Ar ₆And L ₁=L ₂The time,

(2-1) s ≠ q and/or p ≠ r, perhaps

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

(2-2-1) L ₁And L ₂Or pyrene separately respectively with Ar ₅And Ar ₆The different positions combination, or (2-2-2) L ₁And L ₂Or pyrene separately respectively with Ar ₅And Ar ₆The same position combination, work as L but get rid of ₁And L ₂Or Ar ₅And Ar ₆All with its 1 with 6 or its 2 and 7 situations about being connected.

Ar ₅, Ar ₆, L ₁And L ₂Concrete example and substituting group identical with above to explanation in the aforementioned formula (1) those.

[0138]

Below illustrate the specific examples of the pyrene derivatives of general formula (5) representative, but specifically be not confined to this.

[0139]

[0140]

The example of multilayer organic El device comprises have multilayered structure (for example anode/hole injection layer/light-emitting layer/negative electrode), (anode/light-emitting layer/electronics injecting layer/negative electrode) and those devices of (anode/hole injection layer // light-emitting layer/electronics injecting layer/negative electrode).

Except that aryl amine derivatives of the present invention, described multilayer also can be chosen wantonly and contain conventional known substances, as required light emission material, dopant, hole injected material and electronics injected material.Organic El device with this multilayered structure can prevent because the brightness that quencher causes and the reduction in work-ing life.If desired, the use that described light emission material, dopant, hole injected material and electronics injected material can be combined with one another.Use hotchpotch mass-energy to make the device that obtains improve photoemissive brightness and photoemissive efficient, further launch a kind of red light or blue light.In addition, in organic El device of the present invention, hole injection layer, light-emitting layer and electronics injecting layer can have the multilayered structure that comprises more than 2 or 2 layers respectively.In these cases, come the layer of the hole injection of self-electrode to be called as the hole injection layer, and accept to be called as hole transmission layer from the layer in the hole of hole injection layer with hole transport to the layer of light-emitting layer.In addition, come the layer of the electron injection of self-electrode to be called as the electronics injecting layer, and transmission is accepted to be called as electron transfer layer from the layer of the electronics of electronics injecting layer with electric transmission to the layer of light-emitting layer.Can according to such as the energy level of used material, thermal resistance and with the adhering various factors of organic thin film layer or metal electrode, optionally use the above each layer.

[0141]

Except that above-mentioned general formula (3)-(5), can comprise the poly-aromatic substance of condensation with the example that aryl amine derivatives one of the present invention is used from the essential substance of light-emitting layer or dopant, as naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene,

, decacyclene, cool (coronene), tetraphenyl cyclopentadiene, pentapheneyl cyclopentadiene, fluorenes, spiral shell fluorenes, 9,10-diphenylanthrancene, 9,10-two (phenyl-ethynyl) anthracene, 1, the derivative of 4-two (9 '-ethynyl anthryl) phenyl and these compounds thereof; The organo-metallic mixture is as three (8-quinophenol (oxine) root closes (quinolinolat)) aluminium, two (2-methyl-8-quinophenol (oxine) root closes)-4-(the phenyl phenol root closes (phenolinat)) aluminium etc.; Triarylamine derivative, styrylamine derivative, diphenyl ethylene derivatives, coumarin derivatives, pyran derivate,  oxazinone derivative, benzothiazole derivant, benzoxazol derivative, benzimidizole derivatives, pyrazines derivatives, cinnamate derivates, diketopyrrolopyrrolecocrystals derivative, acridone derivatives, quinacridone (quinacridon) derivative etc.; But specifically be not defined in this.

[0142]

The hole injected material preferably is made up of compound, described compound has better cavity transmission ability and has acceptance from the ability in the hole of anode injection with the remarkable ability of hole injection on light-emitting layer or the light emission material, the excited particles that can stop light-emitting layer to produce moves on electronics injecting layer or the electronics injected material, and presents superior film forming ability.The specific examples of hole injected material comprises phthalocyanine derivates, naphthalene cyanines (naphthalocyanine) derivative, fore-telling quinoline derivant,  azoles,  diazole, triazole, imidazoles, imidazolone, imidazole thione (thione), pyrazoline, pyrazolone, imidazolidine, hydrazone, acyl group hydrazone, poly-aromatic yl paraffin, toluylene, divinyl, p-diaminodiphenyl-type triphenylamine, styrylamine-type triphenylamine, diamines-type triphenylamine and derivative thereof; and polyvinyl carbazole, polysilane and macromolecular material; as electronically-conductive polymers, but specifically be not defined in this.

[0143]

In those hole injected materials that use in organic El device of the present invention, more effective hole injected material is aromatic uncle amine derivative and phthalocyanine derivates.

The specific examples of aromatic uncle amine derivative comprises triphenylamine, front three aniline, the tolyl diphenylamine, N, N '-phenylbenzene-N, N '-(3-aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines, N, N, N ', N '-(4-aminomethyl phenyl)-1,1 '-phenyl-4,4 '-diamines, N, N, N ', N '-(4-aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines, N, N '-phenylbenzene-N, N '-dinaphthyl-1,1 '-xenyl-4,4 '-diamines, N, N '-(aminomethyl phenyl)-N, N '-(4-n-butylphenyl)-Fei-9, the 10-diamines, N, N-two (4-two-4-tolyl aminophenyl)-4-phenyl-cyclohexane-and oligomer and polymer with these aromatic uncle amine skeletons, but specifically be not defined in this.

[0144]

The specific examples of phthalocyanine (Pc) derivative comprises phthalocyanine derivates, as H ₂Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc and naphthalene cyanines (naphthalocyanine) derivative, but specifically be not defined in this.

In organic El device of the present invention, between described light-emitting layer and anode, also be preferably formed one and for example contain the above-mentioned hole transmission layer of those aromatic uncle amine derivatives and/or phthalocyanine derivates or the layer of hole injection layer.

[0145]

The electronics injected material preferably is made up of compound, described compound has good electron transport ability and has acceptance and is expelled to superior ability on light-emitting layer or the light emission material from the ability of the electronics of negative electrode injection with electronics, the excited particles that can stop light-emitting layer to produce moves to the hole injection layer, and presents superior film forming ability.The specific examples of electronics injected material comprises Fluorenone, anthraquinone bismethane (anthraquinodimethane), two benzoquinones, thiapyran dioxide,  azoles,  diazole, triazole, imidazoles, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and derivative thereof but specifically is not defined in this.In addition, for strengthening its susceptibility, can respectively electronics be accepted material and electronics supply material and join in described hole injected material and the electronics injected material.

[0146]

In these electronics injected materials that use in organic El device of the present invention, more effective electronics injected material is metal composite compound and the five-ring derivative with nitrogen-atoms.

The specific examples of described metal composite compound comprises that 8-quinophenol (oxine) root closes lithium, two (8-quinophenol (oxine) root closes) zinc, two (8-quinophenol (oxine) root closes) copper, two (8-quinophenol (oxine) root closes) manganese, three (8-quinophenol (oxine) root closes) aluminium, three (2-methyl-8-quinophenol (oxine) root closes) aluminium, three (8-quinophenol (oxine) root closes) gallium, two (10-hydroxy benzo [h] quinoline root closes) beryllium, two (10-hydroxy benzo [h] quinoline root closes) zinc, two (2-methyl-8-quinophenol (oxine) root closes) gallium chloride, two (2-methyl-8-quinophenol (oxine) root closes) (the ortho-cresol root closes (o-cresolato)) gallium, two (2-methyl-8-quinophenol (oxine) root closes) (1-naphthols root closes (naphtholato)) aluminium, two (2-methyl-8-quinophenol (oxine) root closes) (the beta naphthal root closes (naphtholato)) gallium, but specifically be not defined in this.

Described five-ring derivative with nitrogen-atoms is the derivative of  azoles, thiazole,  diazole, thiadiazoles or triazole preferably.The specific examples of described nitrogenous five-ring derivative comprises 2,5-two (1-phenyl)-1,3,4- azoles, dimethyl POPOP, 2,5-two (1-phenyl)-1,3, the 4-thiazole, 2,5-two (1-phenyl)-1,3,4- diazole, 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1; 3; 4- diazole; 2,5-two (1-naphthyl)-1,3; 4- diazole; 1,4-two [2-(5-phenyl  di azoly)] benzene, 1,4-two [2-(5-phenyl  di azoly)-4-tert.-butylbenzene], 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1,3; 4-thiadiazoles; 2; 5-two (1-naphthyl)-1,3,4-thiadiazoles; 1; 4-two [2-(5-phenyl thiadiazolyl group)] benzene, 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1; 3,4-triazole; 2,5-two (1-naphthyl)-1; 3; 4-triazole and 1,4-two [2-(5-Phenyltriazole base)] benzene, but specifically be not defined in this.

[0147]

In organic El device of the present invention, except that the aryl amine derivatives of general formula (1) representative, described light-emitting layer also can be chosen wantonly and contain at least a following material that is selected from: light emission material, dopant, hole injected material and electronics injected material.For strengthening the stability to temperature, humidity, air etc., organic El device of the present invention also can have a protective layer on its surface, perhaps with protections such as its integral part silicone oil, resins.

The anode of organic El device of the present invention can be suitable for making greater than the conducting material of 4eV with having free energy.The example of described anodic conducting material comprises carbon, aluminium, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium and alloy thereof, is used as the metal oxide (as stannic oxide and Indium sesquioxide) and the organic conductive resin of ITO substrate (substrates) or NESA substrate, as Polythiophene and polypyrrole.The negative electrode of organic El device of the present invention can be suitable for making with having the following conducting material of free energy 4eV or 4eV.The example of the conducting material of described negative electrode comprises magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminium, lithium fluoride and alloy thereof, but specifically is not defined in this.The representative instance of described alloy comprises magnesium and the alloy of alloy, magnesium and the indium of silver and the alloy of lithium and aluminium, but specifically is not defined in this.Can control the ratio of forming in the described alloy between the metal, described ratio is suitable for determining according to the temperature in vapor deposition (vapordeposition) source, atmosphere, vacuum tightness etc.If desired, anode and negative electrode can constitute more than two-layer or two-layer.

[0148]

At least one surface of organic El device of the present invention preferably presents enough transparencies in photoemissive wavelength region, to strengthen its light emission efficient.In addition, the substrate of described device is also preferably transparent.This transparency electrode adopts above-mentioned conducting material through formation such as gas-phase deposition method, sputtering methods, thereby has guaranteed desired transparence.The electrode of laying on the light emission surface of described device preferably has 10% or above transparence.Described substrate does not specifically limit, as long as it has favorable mechanical and hot strength and transparence is promptly suitable preferably.The example of described substrate comprises glass substrate and transparent resin film.The specific examples of transparent resin film comprises by polyethylene, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, polyvinyl alcohol, polyethylene butyraldehyde (butyral), nylon, polyether-ether-ketone, polysulfones, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether multipolymer, fluorinated ethylene propylene, tetrafluoroethylene-ethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, poly(vinylidene fluoride), polyester, polycarbonate, polyurethane(s), pi, inferior acid amides of polyethers and polypropylene.

[0149]

Each of organic El device of the present invention layer can form method (as vacuum coating method, sputtering method, plasma and ion plating) or wet film formation method (as rotation coating method, pickling process and mobile coating method) forms by dry film.The thickness of each layer does not specifically limit, but should be adjusted to suitable scope.When thickness is too big, must apply bigger voltage to reach predetermined light output to this device, the result causes light emission efficient to reduce.On the other hand, when thickness too hour, in each layer, easily form pin hole, even make and apply electric field thereon, can not obtain enough photoemissive brightness.The common scope of suitable thickness of each layer is 5nm to 10 μ m, preferred 10nm to 0.2 μ m.

In wet film formation method, with form the material dissolves of each layer or be scattered in suitable solvent such as ethanol, chloroform, tetrahydrofuran (THF) and dioxane in, form its film.Forming the used solvent of each layer does not specifically limit.Also resin or the additive that is fit to can be joined in each organic thin film layer, in the film that obtains, form pin hole etc. to improve film formed character, prevention.The example of the resin that uses for above-mentioned purpose comprises insulating resin, as polystyrene, polycarbonate, polyarylate, polyester, polymeric amide, polyurethane(s), polysulfones, polymethylmethacrylate, polymethyl acrylate and cellulose family and multipolymer thereof, the photoconduction resin, as poly N-vinyl carbazole and polysilane, and electricity leads resin, as Polythiophene and polypyrrole.The example of additive comprises antioxidant, UV light absorber and softening agent.

[0150]

Organic El device of the present invention is suitable for for example dull and stereotyped photocell, as flat-panel monitor of on-wall type televisor etc., the light source of duplicating machine, printer, liquid-crystal display, and the back side light source of surveying instrument, display panel, mark lamp (marker light) etc.In addition, material of the present invention not only can be used for also can having other purposes in the organic El device, as electrophotographic member, photoelectric commutator element, solar cell, mage reconstructor tube sensor etc.

Embodiment

[0151]

Describe the present invention in detail by reference the following example.

Synthetic embodiment 1(synthesizing of chemical compound (4))

(1-1) 2-bromo-6-methylnaphthalene is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add trifluoromethanesulfonic acid-6-bromo-2-naphthyl ester of 32g (90mmol), dichloride (diphenyl phosphine ferrocene) palladium of 3.6g (5% mole), lithiumbromide and the 100mL exsiccant tetrahydrofuran (THF) of 7.8g (90mmol), the solution that obtains is cooled to-20 ℃ then.After in this flask, adding 90mL (90mmol, 1mol/L (tetrahydrofuran (THF))) methyl-magnesium-bromide at leisure, the solution that obtains was stirred 4 hours 80 ℃ of heating the time.Behind the reaction terminating, in this reaction soln, add 100mL dilute hydrochloric acid, separate organic layer,, then use dried over mgso with sodium hydrogen carbonate solution and sodium chloride solution washing.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=90/10) purifying, obtain 9.4g target compound (white crystal) (yield: 47%).

(1-2) 2-(6-methyl-2-naphthyl) phenyl aldehyde is synthetic

Under argon gas stream; in the 500mL three-necked flask that is equipped with prolong, add the 2-bromo-6-methylnaphthalene of 6.6g (30mmol), the 2-formyl radical phenyl-boron dihydroxide of 5.4g (36mmol), four (triphenyl phosphine) palladium, 45mL 2N aqueous sodium carbonate and the 90mL glycol dimethyl ether of 0.7g (0.6mmol), with the vlil that obtains 8 hours.Behind the reaction terminating, in this reaction soln, add 100mL water, separate organic layer,, then use dried over mgso with the sodium chloride solution washing.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=60/40) purifying, obtain 6.7g target compound (white crystal) (yield: 91%).

[0152]

(1-3) 2-((2-methoxy-ethylene base) phenyl)-6-methylnaphthalene is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 13.7g (55mmol) 2-(6-methyl-2-naphthyl) phenyl aldehyde, (potassium tert.-butoxide and the 250mL exsiccant tetrahydrofuran (THF) of methoxymethyl) San Ben Phosphonium, 7.5g (67mmol) at room temperature stir the solution that obtains then and spend the night in the chlorination of 21g (61mmol).Behind the reaction terminating, in this reaction soln, add 100mL water, separate organic layer, then use dried over mgso.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=10/90) purifying, obtain 12.8g target compound (white crystal) (yield: 84%).

(1-4) 2-methyl Synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 2-((2-methoxy-ethylene base) phenyl)-6-methylnaphthalene of 12.8g (46mmol), several formic acid and 100mL exsiccant methylene dichloride, under the room temperature, with the solution stirring that obtains 8 hours.Behind the reaction terminating, in this reaction soln, add 100mL sodium hydrogen carbonate solution, filtering separation crystal.With crude product water and the methanol wash that obtains, vacuum-drying 8 hours under 50 ℃ of temperature then obtains 8.2g target compound (white crystal) (yield: 73%).

[0153]

(1-5) 2-methyl-6, the 12-dibromo

Synthetic

Under argon gas stream, in the 1L three-necked flask that is equipped with prolong, add the 2-methyl of 8.2g (34mmol)

, 14.5g (81mmol) N-bromine succinimide and 400mL N, dinethylformamide at room temperature stirs a night with the solution that obtains then.Behind the reaction terminating, in this reaction soln, add 300mL water, filtering separation crystal.With crude product water and the methanol wash that obtains, use 100mL toluene recrystallization then, obtain 8.8g target compound (white crystal) (yield: 65%).

(1-6) chemical compound (4) is synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-methyl-6 of 4.0g (10mmol), the 12-dibromo , 5.6g (25mmol) two (3, the 4-3,5-dimethylphenyl) amine, O.03g acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole) of (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 5.8g buff powder.Determine that according to the field result that mass spectrum (FieldDesorption MaSS Spectrum) (FD-MS) measures that dissociates this pale yellow powder is compound (4) (yield: 85%).

Adopt methylene dichloride as solvent, measure by DRX-500 (trade(brand)name: Brucker OpticsInc produces), the compound that obtains (4) ¹The results are shown in Figure shown in 1 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (4) in toluene solvant is respectively 400nm and 456nm.

[0154]

Synthetic embodiment 2(synthesizing of compound (9))

(2-1) 2-sec.-propyl-6, the 12-dibromo Synthetic

Press synthetic embodiment 1 step (1-1) to the similar mode of step (1-5), but, obtain target compound with the methyl-magnesium-bromide in the sec.-propyl bromination magnesium replacement step (1-1).

(2-2) compound (9) is synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-sec.-propyl-6 of 4.2g (10mmol), the 12-dibromo , the 4-isopropyl phenyl para-totuidine of 5.6g (25mmol), O.03g acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole) of (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.4g buff powder.Determine that according to FD-MS mensuration the product that obtains is compound (9) (yield: 90%).

Adopt methylene dichloride as solvent, measure by DRX-500 (trade(brand)name: Brucker OpticsInc makes), the compound that obtains (9) ¹The results are shown in Figure shown in 2 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (9) in toluene solvant is respectively 407nm and 453nm.

[0155]

Synthetic embodiment 3(synthesizing of chemical compound (20))

(3-1) 2-bromo-6-isopropyl naphthalene is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add trifluoromethanesulfonic acid-6-bromo-2-naphthyl ester of 32g (90mmol), dichloride (diphenyl phosphine ferrocene) palladium of 3.6g (5% mole), lithiumbromide and the 100mL exsiccant tetrahydrofuran (THF) of 7.8g (90mmol), the solution that obtains is cooled to-20 ℃ then.The sec.-propyl bromination magnesium that adds 90mL (90mmol, 1mol/L (tetrahydrofuran (THF))) in this flask at leisure under 80 ℃, stirs the solution that obtains 4 hours under heating.Behind the reaction terminating, in this reaction soln, add 100mL dilute hydrochloric acid, separate organic layer,, then use dried over mgso with sodium hydrogen carbonate solution and sodium chloride solution washing.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=90/10) purifying, obtain 9.4g target compound (white crystal) (yield: 33%).

(3-2) 6-isopropyl naphthalene-2-boric acid is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 2-bromo-6-isopropyl naphthalene, 100mL exsiccant ether and the 50mL exsiccant toluene of 9.4g (38mmol), the solution that obtains is cooled to-40 ℃ then.In this flask, slowly be added dropwise to the n-Butyl Lithium of 25mL (40mmol, 1.58M (normal hexane)), under-20 ℃ of temperature, with the solution stirring that obtains 2 hours.Then this solution is cooled to-40 ℃, slowly is added dropwise to 26mL (114mmol) tri-isopropylborate then, under the room temperature, 1 night of solution stirring that obtains.Behind the reaction terminating, in this reaction soln, add 100mL dilute hydrochloric acid, separate organic layer,, then use dried over mgso with the sodium chloride solution washing.Use the rotatory evaporator distillation to remove and desolvate,, obtain 5.0g target compound (white crystal) (yield: 63%) the crude product that obtains 100mL toluene wash.

[0156]

(3-3) 5-sec.-propyl-2-(6-sec.-propyl-2-naphthyl) phenyl aldehyde is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 2-hydroxyl-5-isopropyl benzene formaldehyde of 4.4g (27mmol), the trifluoromethanesulfanhydride anhydride of 11.2g (40mmol), the pyridine of 6mL (80mmol) and the methylene dichloride of 100mL, then the solution that obtains was at room temperature stirred 2 hours.Behind the reaction terminating, the filtering separation resultant, with hexane and washed with dichloromethane, vacuum-drying 8 hours under 50 ℃ of temperature then obtains 6.0g 2-formyl radical-4-isopropyl phenyl triflate (white crystal) (yield: 75%) with the crude product that obtains.Then; under argon gas stream; in the 500mL three-necked flask that is equipped with prolong, add 2-formyl radical-4-isopropyl phenyl triflate of 5.9g (20mmol), 6-isopropyl naphthalene-2-boric acid of 4.7g (22mmol), four (triphenyl phosphine) palladium, 30mL 2N aqueous sodium carbonate and the 40mL glycol dimethyl ether of 1.1g (1mmol), with the vlil that obtains 8 hours.Behind the reaction terminating, in this reaction soln, add 100mL water, separate organic layer,, then use dried over mgso with the sodium chloride solution washing.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=60/40) purifying, obtain 4.4g target compound (white crystal) (yield: 70%).

(3-4) 2-sec.-propyl-6-(4-sec.-propyl-2-(2-methoxy-ethylene base) phenyl) naphthalene is synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 4.4g (14mmol) 5-sec.-propyl-2-(6-sec.-propyl-2-naphthyl) phenyl aldehyde, (potassium tert.-butoxide and the 100mL exsiccant tetrahydrofuran (THF) of methoxymethyl) San Ben Phosphonium, 1.7g (15mmol) at room temperature stir a night with the solution that obtains then in the chlorination of 5.1g (15mmol).Behind the reaction terminating, in this reaction soln, add 100mL water, separate organic layer, then use dried over mgso.Use the rotatory evaporator distillation to remove and desolvate, then with the crude product that obtains through column chromatography (silica gel, hexanes/ch=10/90) purifying, obtain 4.3g target compound (white crystal) (yield: 90%).

[0157]

(3-5) 2, the 8-di-isopropyl Synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add 2-sec.-propyl-6-(4-sec.-propyl-2-(2-methoxy-ethylene base) phenyl) naphthalene of 4.3g (12mmol), several formic acid and 50mL exsiccant methylene dichloride, under the room temperature, with the solution stirring that obtains 8 hours.Behind the reaction terminating, in this reaction soln, add 100mL sodium hydrogen carbonate solution, filtering separation crystal.With crude product water and the methanol wash that obtains, vacuum-drying 8 hours under 50 ℃ of temperature then obtains 3.5g target compound (white crystal) (yield: 90%).

(3-6) 2,8-di-isopropyl-6,12-dibromo Synthetic

Under argon gas stream, in the 500mL three-necked flask that is equipped with prolong, add 2 of 3.5g (12mmol), the 8-di-isopropyl , 5.3g (30mmol) N monobromo succinimide and 20mlN, dinethylformamide at room temperature stirs a night with the solution that obtains then.Behind the reaction terminating, in this reaction soln, add 300mL water, filtering separation crystal.With crude product water and the methanol wash that obtains, use 100mL toluene recrystallization then, obtain 4.7g target compound (white crystal) (yield: 80%).

(3-7) chemical compound (20) is synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add 2 of 4.7g (10mmol), 8-di-isopropyl-6,12-dibromo

, the 4-isopropyl phenyl para-totuidine of 5.6g (25mmol), the acid chloride of 0.03g (1.5% mole), the tri-butyl phosphine of 0.06g (3% mole), sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol), under l00 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.6g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (20) (yield: 88%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (20) ¹The results are shown in Figure shown in 3 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (20) in toluene solvant is respectively 407nm and 450nm.

[0158]

Synthetic embodiment 4(synthesizing of compound (23))

(4-1) the 2-tertiary butyl-8-sec.-propyl-6, the 12-dibromo Synthetic

Press synthetic embodiment 3 steps (3-1) to the similar mode of step (3-6), but, obtain target compound with the 2-hydroxyl-5-isopropyl benzene formaldehyde in 2-hydroxyl-5-tert.-butylbenzene formaldehyde replacement step (3-3).

(4-2) compound (23) is synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-tertiary butyl-8-sec.-propyl-6 of 4.8g (10mmol), the 12-dibromo , 5.6g (25mmol) two (3, the 4-3,5-dimethylphenyl) amine, the O.03g acid chloride, the tri-butyl phosphine of 0.06g (3% mole), sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.9g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (23) (yield: 90%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (23) ¹The results are shown in Figure shown in 4 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (23) in toluene solvant is respectively 409nm and 453nm.

[0159]

Synthetic embodiment 5(synthesizing of compound (25))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-sec.-propyl-6 that obtains in the step (2-1) of synthetic embodiment 2 of 4.2g (1Ommol), the 12-dibromo

6.3g (25mmol) two (3, the 4-3,5-dimethylphenyl) acid chloride of amine, 0.03g (1.5% mole), the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.8g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (25) (yield: 88%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (25) ¹The results are shown in Figure shown in 5 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (25) in toluene solvant is respectively 415nm and 459nm.

[0160]

Synthetic embodiment 6(synthesizing of compound (39))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-sec.-propyl-6 that obtains in the step (2-1) of synthetic embodiment 2 of 4.2g (10mmol), the 12-dibromo 6.7g two (2-naphthyl) amine (25mmol), the acid chloride of 0.03g (1.5% mole), the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.8g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (39) (yield: 85%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (39) ¹The results are shown in Figure shown in 6 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (39) in toluene solvant is respectively 408nm and 452nm.

[016l]

Synthetic embodiment 7(synthesizing of compound (57))

(7-1) the 2-tertiary butyl-6, the 12-dibromo

Synthetic

Press synthetic embodiment 1 step (1-1) to the similar mode of step (1-5), but, obtain target compound with the methyl-magnesium-bromide in the tertiary butyl bromination magnesium replacement step (1-1).

(7-2) compound (57) is synthetic

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-tertiary butyl 6 of 4.4g (10mmol), the 12-dibromo , 5.6g (25mmol) two (3, the 4-3,5-dimethylphenyl) sodium tert-butoxide and the 100mL exsiccant toluene of the tri-butyl phosphine of the acid chloride of amine, 0.03g (1.5% mole), 0.06g (3% mole), 2.4g (25mmol), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.5g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (57) (yield: 90%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (57) ¹The results are shown in Figure shown in 7 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (57) in toluene solvant is respectively 410nm and 456nm.

[0162]

Synthetic embodiment 8(synthesizing of compound (95))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-methyl-6 that obtains in the step (1-5) of synthetic embodiment 1 of 4.0g (10mmol), the 12-dibromo , two (4-cyclohexyl phenyl) amine of 8.3g (25mmol), the acid chloride of 0.03g (1.5% mole), the tri-butyl phosphine of 0.06g (3% mole), sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 6.3g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (95) (yield: 70%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (95) ¹The results are shown in Figure shown in 8 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (95) in toluene solvant is respectively 406nm and 454nm.

[0163]

Synthetic embodiment 9(synthesizing of compound (D-973))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add 6 of 3.8g (10mmol), the 12-dibromo

, 2.7g (25mmol) acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole) of methylphenylamine, 0.03g (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 2.2g white powder.Measure according to FD-MS, determine that the product that obtains is compound (D-973) (yield: 50%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (D-973) ¹The results are shown in Figure shown in 9 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (D-973) in toluene solvant is respectively 373nm and 440nm.

[0164]

Synthetic embodiment 1O(synthesizing of compound (D-974))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add 6 of 3.8g (10mmol), the 12-dibromo , 3.4g (25mmol) acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole) of N-isopropyl aniline, 0.03g (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 2.0g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (D-974) (yield: 40%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (D-974) ¹The results are shown in shown in Figure 10 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (D-974) in toluene solvant is respectively 362nm and 436nm.

[0165]

Synthetic embodiment 11(synthesizing of compound (D-998))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add 6 of 3.8g (10mmol), the 12-dibromo , N-(4-isopropyl phenyl) pyridine-3-amine of 5.3g (25mmol), O.03g acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (3% mole) of (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 4.2g white powder.Measure according to FD-MS, determine that the product that obtains is compound (D-998) (yield: 65%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (D-998) ¹The results are shown in shown in Figure 11 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (D-998) in toluene solvant is respectively 393nm and 444nm.

[0166]

Synthetic embodiment 12(synthesizing of compound (D-1000))

Under argon gas stream, in the 300mL three-necked flask that is equipped with prolong, add the 2-methyl-6 of 3.9g (10mmol), the 12-dibromo

, N-(4-isopropyl phenyl) pyridine-3-amine of 5.3g (25mmol), O.03g acid chloride, the O.06g tri-butyl phosphine, sodium tert-butoxide and the 100mL exsiccant toluene of 2.4g (25mmol) of (30% mole) of (1.5% mole), under 100 ℃ of temperature heating, with one night of solution stirring that obtains.Behind the reaction terminating, the sedimentary crystal of filtering separation with 50mL toluene and 100mL methanol wash, obtains the 5.3g buff powder.Measure according to FD-MS, determine that the product that obtains is compound (D-1000) (yield: 80%).

Adopt methylene dichloride as solvent, measure through DRX-500 (trade(brand)name: Brucker Optics Inc produces), the compound that obtains (D-1000) ¹The results are shown in shown in Figure 12 of H-NMR collection of illustrative plates.In addition, maximum absorption wavelength and the maximum fluorescence wavelength of compound (D-1000) in toluene solvant is respectively 385nm and 440nm.

[0167]

Embodiment 1

On the glass baseplate of one 25mm * 75mm * 1.1mm, form the thick transparency electrode of making by Indium sesquioxide of 120nm.This is had the glass baseplate uviolizing and the ozone clean of transparency electrode.The glass baseplate that has transparency electrode that will clean then is fixed on a vacuum vapor deposition apparatus.

At first, with N '; N "-two [4-(diphenyl amino) phenyl]-N ', N "-phenylbenzene xenyl-4, the vapor deposition of 4 '-diamines forms the hole injection layer with 60nm thickness; vapor deposition N on this hole injection layer then; N, N ', N '-four (4-xenyl)-4; 4 '-bendizine forms the hole transmission layer with 20nm thickness.Then, on this hole transmission layer, with weight ratio 40: 2 vapor deposition 10,10 '-two simultaneously [1,1 ', 4 ', 1 "] terphenyl-2-base-9,9 '-dianthranide (bianthracenyl) and above-claimed cpd (9), formation has the light-emitting layer of 40nm thickness.

Then, vapor deposition three on this light-emitting layer (8-quinophenol (oxine) root closes) aluminium forms the electronics injecting layer with 10nm thickness.On this electronics injecting layer, with weight ratio vapor deposition in 10: 0.3 three (8-quinophenol (oxine) root closes) aluminium and lithium, form one deck of 10nm thickness, thereon again vapor deposition aluminium to form the aluminium lamination of 150nm thickness.The function of this aluminium lamination is a negative electrode.Make an organic El device thus.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.0V and current density 10mA/cm ²Down, emission brightness is 602cd/m ²(photoemissive spike is long: be the blue light of 6.0cd/A with current efficiency 464nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 18900 hours.

[0168]

Embodiment 2

The identical method of carrying out according to embodiment 1, but replace compound (9) with compound (23), make an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.5V and current density 10mA/cm ²Down, emission brightness is 664cd/m ²(photoemissive spike is long: be the blue light of 6.6cd/A with current efficiency 462nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 16000 hours.

[0169]

Embodiment 3

The identical method of carrying out according to embodiment 1, but with 10-(3-(naphthalene-1-yl) phenyl)-9-(naphthalene-2-yl) anthracene [1,1 ', 4 ', 1 "] terphenyl-2-base-9 that replaces 10,10 '-two, 9 '-dianthranide is made an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.5V and current density 10mA/cm ²Down, emission brightness is 631cd/m ²(photoemissive spike is long: be the blue light of 6.3cd/A with current efficiency 464nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 20000 hours or longer.

[0170]

Embodiment 4

The identical method of carrying out according to embodiment 3, but replace compound (9) as dopant with compound (23), make an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.5V and current density 10mA/cm ²Down, emission brightness is 710cd/m ²(photoemissive spike is long: be the blue light of 7.1cd/A with current efficiency 465nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 20000 hours or longer.

[0171]

Embodiment 5

The identical method of carrying out according to embodiment 3, but replace compound (9) as dopant with compound (25), make an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.5V and current density 10mA/cm ²Down, emission brightness is 793cd/m ²(photoemissive spike is long: be the blue light of 7.9cd/A with current efficiency 469nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 20000 hours or longer.

[0172]

Embodiment 6

The identical method of carrying out according to embodiment 3, but replace compound (9) as dopant with compound (10), make an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.5V and current density 10mA/cm ²Down, emission brightness is 782cd/m ²(photoemissive spike is long: be the blue light of 7.8cd/A with current efficiency 468nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 20000 hours or longer.

[0173]

The comparative example 1

The identical method of carrying out according to embodiment 1, but with 6,12-two (the 4-isopropyl phenyl-to toluino) Replace compound (9), make an organic El device.

The organic El device that so obtains is seen through electric current detect, confirm at voltage 6.3V and current density 10mA/cm ²Down, emission brightness is 594cd/m ²(photoemissive spike is long: be the blue light of 5.9cd/A with current efficiency 462nm).With this device by the beginning brightness be 500cd/m ²The place begins to carry out persistence by the DC electric current to be detected, and confirms that its half life is 4590 hours.

Obviously find out from above result: when any substituting group not with diamino

Skeleton structure in conjunction with the time be bonded to each other because each is changed between house thing, half life, shorten.

Commercial Application

[0l74]

Use organic EL device of aryl amine derivatives of the present invention in addition under very low voltage also Demonstrate the upper enough brightness of practice, and have the luminous efficiency of increase, and this device exists Therefore the character that does not occur deterioration after long-time the use have the characteristic in long service life. Therefore, this EL device can be used as the dull and stereotyped photocell of on-wall type television set or is used as aobvious The light source that shows the back light of device.

Claims

1. aryl amine derivatives by following general formula (1) representative:

A wherein ₁To A ₄The independent separately hydrogen atom of representing, have 1-50 carbon atom replacement or unsubstituted alkyl, replacement or unsubstituted aryl with 5-50 ring carbon atom, replacement or unsubstituted aralkyl with 6-50 ring carbon atom, replacement or unsubstituted cycloalkyl with 3-50 ring carbon atom, replacement or unsubstituted alkoxyl group with 1-50 ring carbon atom, replacement or unsubstituted aryloxy with 5-50 ring carbon atom, replacement or unsubstituted virtue amino with 5-50 ring carbon atom, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 3-50 ring carbon atom replacement or unsubstituted heterocyclic, have 3-50 carbon atom replacement or unsubstituted silyl or halogen atom;

But get rid of all R in the general formula (1) ₁To R ₄It all is the situation of hydrogen atom.

2. according to the aryl amine derivatives of claim 1, R in its formula of (1) ₁Or R ₃In at least one independently represent replacement with 1-50 carbon atom or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 6-50 ring carbon atom replacement or unsubstituted aralkyl or have replacement or the unsubstituted cycloalkyl of 3-50 ring carbon atom.

3. according to the aryl amine derivatives of claim 1, R in its formula of (1) ₁And R ₃Independent separately representative have 1-50 carbon atom replacement or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 6-50 ring carbon atom replacement or unsubstituted aralkyl or have replacement or the unsubstituted cycloalkyl of 3-50 ring carbon atom.

4. according to the aryl amine derivatives of claim 1, R in its formula of (1) ₂Or R ₄In at least one independently represent replacement with 1-50 carbon atom or unsubstituted primary alkyl, have 1-50 carbon atom replacement or unsubstituted secondary alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 1-50 ring carbon atom replacement or unsubstituted aralkyl or have replacement or the unsubstituted cycloalkyl of 3-50 ring carbon atom.

5. according to the aryl amine derivatives of claim 1, R in its formula of (1) ₁To R ₄Independently separately represent hydrogen atom, have 5-20 ring carbon atom replacement or unsubstituted arylamino, have 1-20 carbon atom replacement or unsubstituted alkyl amino, have 3-50 ring carbon atom replacement or unsubstituted heterocyclic or have replacement or the unsubstituted silyl of 3-50 carbon atom.

6. aryl amine derivatives by following general formula (2) representative:

A wherein ₅To A ₈Independent separately representative have 1-50 carbon atom replacement or unsubstituted alkyl, have 5-50 ring carbon atom replacement or unsubstituted aryl, have 3-50 ring carbon atom replacement or unsubstituted cycloalkyl or have 3-50 ring carbon atom replacement or unsubstituted heterocyclic;

7. according to each aryl amine derivatives among the claim 1-6, it is a kind of dopant that is used for Organnic electroluminescent device.

8. Organnic electroluminescent device, it comprises at least a organic thin film layer, this thin film layer comprises the light-emitting layer that is clipped between the electrode pair that anode and negative electrode form, and wherein at least a described organic thin film layer comprises among the single claim 1-6 each aryl amine derivatives or its mix ingredients.

9. Organnic electroluminescent device according to Claim 8, wherein said light-emitting layer comprise among the single claim 1-6 each aryl amine derivatives or its mix ingredients.

10. Organnic electroluminescent device according to Claim 8, wherein said light-emitting layer comprise its amount and are each aryl amine derivatives among the claim 1-6 of 0.1-20% weight.

11. Organnic electroluminescent device according to Claim 8, it launches blue light.