CN101171224A

CN101171224A - Novel organic electroluminescent material, organic electroluminescent element using the same, and solution for forming thin film for organic electroluminescence

Info

Publication number: CN101171224A
Application number: CNA2006800156672A
Authority: CN
Inventors: 井上哲也; 近藤浩史; 顺毛直宪
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2005-05-09
Filing date: 2006-04-20
Publication date: 2008-04-30

Abstract

The present invention provides an aromatic amine compound having a specific structure and an organic electroluminescent element comprising an organic thin film layer comprising one or more layers sandwiched between a pair of electrodes comprising an anode and a cathode, wherein at least one of the layers contains the aromatic amine compound, and thus provides an organic electroluminescent element using the organic thin film layer, particularly an organic electroluminescent element exhibiting various luminescent colors, high heat resistance, long life, high luminescent luminance, and high luminescent efficiency, and provides a novel aromatic amine compound having high solubility and capable of forming a film in a wet process and a solution for forming a thin film for organic electroluminescent element.

Description

Novel electroluminescent material, the organic electroluminescent device that uses this material and organic electroluminescent are used with film and are formed solution

Technical field

The present invention relates to a kind of aromatic amines compound and use the organic electroluminescent device of this compound, especially present various luminous tones, thermotolerance height, the life-span is long, luminosity is high and luminous efficiency is high organic electroluminescent device, provide in order to realize this organic electroluminescent device a kind of solvability height, can be in the wet type process film forming new aromatic amine compound and organic electroluminescent with film with forming solution.

Background technology

Organic electroluminescent (EL) element of use organic substance is used as the light source of the flat luminous body of wall hung television or the backlight of indicating meter etc., is just developed energetically.1963, Pope etc. observe the electroluminescence phenomenon (non-patent literature 1) of organic substance in anthracene single crystal, nineteen sixty-five, the gorgeous pond of He Lu (Helfrich) successfully observes strong injection type EL (non-patent literature 2) with Si Chaneide (Schneider) by using the good solution electrode system of injection efficiency.Such as so far report, utilizing conjugation organic substrate (host) material and conjugation organic activator to form the research of organic luminous material with condensation phenyl ring, as the organic substrate material, for example can enumerate naphthalene, anthracene, phenanthrene, tetracene, pyrene, benzopyrene,

(chrysene), Pi, carbazole, fluorenes, biphenyl, terphenyl, benzophenanthrene oxide compound, dihalobiphenyl, anti-(trans)-stilbene and 1,4-diphenyl diethylene etc. as activator, for example can be enumerated anthracene, tetracene and pentacene etc.But these organic light emission materials all exist as having the simple layer that surpasses 1 μ m thickness, and high electric field is essential when luminous.So, utilize the research of the thin-film component of vacuum deposition method to be carried out (for example non-patent literature 3).But filming is effectively in the attenuating of driving voltage, but also is unlikely to obtain the element of the high brightness of realistic scale.Therefore, Tang etc. have designed under vacuum deposition the organic EL of stacked 2 films (hole transporting layer and luminescent layer) as thin as a wafer between anode and negative electrode, have realized high brightness (non-patent literature 4 or patent documentation 1) with low driving voltage.Then, carried out the exploitation to the organic compound that uses in hole transporting layer and the luminescent layer between many decades, the result has realized the life-span and the luminous efficiency of practicability level.As a result, organic EL begins to be practical from display part of car stereo (car stereo), mobile telephone etc.

But, aspect practical, relatively luminosity, long-time use through the time deterioration weather resistance etc. insufficient, and then require further to be enhanced.

As the means that address these problems, inject the conveying material as the hole, can use oligomer (3 polymers, 4 polymers) amine in order to improve second-order transition temperature (Tg).The compound of following general formula (A) expression is for example disclosed in patent documentation 2.

[changing 1]

(in the formula, R ₁, R ₂, R ₃Be same to each other or different to each other expression hydrogen atom, low alkyl group, lower alkoxy, R ₄Expression hydrogen atom, low alkyl group, lower alkoxy or chlorine atom.With

[changing 2]

A uses

Expression, R ₅Expression low alkyl group, lower alkoxy, chlorine atom.)

[changing 3]

The compound of following general formula (C) expression is disclosed in patent documentation 4.

[changing 4] expression

(R ₀₁～R ₀₄Be And

Any one, Ф represents phenylene, R ₀₁, R ₀₂, R ₀₃And R ₀₄Represent the ammonia diaryl base phenylene respectively, r ₀₁, r ₀₂, r ₀₃And r ₀₄Represent 0～5 integer respectively, r ₀₁+ r ₀₂+ r ₀₃+ r ₀₄Be more than 1.R ₁₁, R ₁₂, R ₁₃, R ₁₄, R ₁₅, R ₁₆And R ₁₇The aryl of representing replacement or non-replacement respectively.)

The compound of following general formula (D) expression is disclosed in patent documentation 5.

[changing 5]

(in the formula, R ¹～R ¹⁸Be respectively the independent respectively base of selecting in the group that constitutes by hydrogen atom, low alkyl group and lower alkoxy)

And then, the compound that following general formula (E) is represented is disclosed in patent documentation 6.

[changing 6]

(Ar ¹～Ar ⁶Aryl for carbonatoms 6～24 in the aryl of carbonatoms 6～24 in the alkyl of hydrogen atom, carbonatoms 1～6 or alkoxyl group, the ring or the ring that can be replaced by styryl.X is a concatenating group, for alkylidene group, diphenylmethylene, ehter bond, the thioether bond of arylalkenyl, the carbonatoms 1～6 of carbonatoms 6～24 in singly-bound, the ring, replace or do not have the vinyl bonds or the heteroaromatic of replacement.R ¹, R ²Be the alkyl of carbonatoms 1～6 or alkoxyl group, hydrogen atom, also can form the replacement that is bonded to each other or not have the five-membered ring or the six membered ring of replacement.)

But the compound of record can not obtain sufficient hole injection in patent documentation 2～6.

In addition, as the method that improves the hole injection, used the compound that imports fluorenyl.For example, in patent documentation 7, disclose the luminous element of the compound shown in the following general formula (F) as hole transporting material.

[changing 7]

(in the formula, R11 represents alkyl or aralkyl, and R12, R13, R14 and R15 represent hydrogen atom, alkyl, alkoxyl group or halogen atom.)

The Tg of this compound is below 100 ℃, uses the life-span weak point of the element of this compound, does not have thermotolerance, can not practicability.

The luminous element of compound shown in the following compound (G) that will improve general formula (F) as hole transporting material disclosed in patent documentation 8.

[changing 8]

Though the raising of the visible second-order transition temperature of this compound, the raising of hole injection, the life-span is still short.

And then, the compound that following general formula (H) is represented is disclosed in patent documentation 9.

[changing 9]

This compound is the as seen raising of hole injection also, but needs raising, the long lifetime of further second-order transition temperature.

Patent documentation 1: No. 4356429 specification sheetss of United States Patent (USP)

Patent documentation 2: No. 3220950 communique of patent

Patent documentation 3: the spy opens the 2000-86595 communique

Patent documentation 4: the spy opens the 2000-156290 communique

Patent documentation 5: the spy opens flat 9-301934 communique

Patent documentation 6: the spy opens the 2000-309566 communique

Patent documentation 7: the spy opens flat 5-25473 communique

Patent documentation 8: the spy opens flat 11-35532 communique

Patent documentation 9: the spy opens the 2000-80433 communique

Non-patent literature 1:J.Chem.Phys., 38 (1963) 2042

Non-patent literature 2:Phys.Rev.Lett., 14 (1965) 229

Non-patent literature 3: solid film (Thin Solid Flims), 94 (1982) 171

Non-patent literature 4:Appl.Phys.Lett., 51 (1987) 913

Summary of the invention

The present invention proposes in order to solve above-mentioned problem just, the organic electroluminescent device that its purpose is to provide a kind of aromatic amines compound and has used this compound, especially present various luminous tones, thermotolerance height, the life-span is long, luminosity is high and luminous efficiency is high organic electroluminescent device, provide in order to realize this organic electroluminescent device a kind of solvability height, can be in the wet type process film forming new aromatic amine compound and organic electroluminescent with film with forming solution.

The inventor etc. concentrate on studies to achieve these goals, found that the aromatic amines compound of following general formula (1) expression can be realized above-mentioned purpose, so that finish the present invention.

That is, the invention provides a kind of aromatic amines compound, it is with following general formula (1) expression,

[changing 10]

In the general formula (1), Ar ₁～Ar ₆Expression replaces or does not have the aryl of carbonatoms 6～40 in the ring of replacement or replace or do not have the heteroaryl of carbonatoms 3～40 in the ring of replacement independently respectively, also has Ar ₁And Ar ₂, and Ar ₅And Ar ₆Also can link by singly-bound respectively and form carbazyl, R ₁～R ₄Represent halogen atom, carboxyl, amino, hydroxyl respectively independently, replace or do not have the carbonatoms 1～40 of replacement alkyl, replace or do not have the carbonatoms 2～40 of replacement alkenyl, replace or do not have replacement carbonatoms 2～40 alkynyl or replace or do not have the alkoxyl group of the carbonatoms 1～40 of replacement, n, m, p and q are respectively 0～4 integer

L is the divalent concatenating group with following general formula (2) and (3) expression,

-(Ar ₇) _n-(Ar ₈) _b-(Ar ₉) _c- (2)

In the general formula (2), Ar ₇～Ar ₉With above-mentioned Ar ₁～Ar ₆Identical, a, b and c are respectively 1～3 integer.

[changing 11]

In the general formula (3), R ₆And R ₇With above-mentioned R ₁～R ₄Identical, and R ₆And R ₇Also can link mutually and form ring structure.

In addition, the present invention also provides a kind of organic EL, and the organic thin film layer that its clamping between anode and negative electrode has one or more layers formation of luminescent layer at least forms, wherein,

One deck at least of this organic thin film layer contains aromatic amines compound as independent or the ingredients of a mixture.Organic EL of the present invention presents various luminous tones, and the thermotolerance height, the life-span is long, luminosity is high and luminous efficiency is high.

And then, the present invention provide in order to realize above-mentioned functions a kind of solvability height, can the film forming new aromatic amine compound of wet type and organic electroluminescent with film with forming solution.

The solvability height of aromatic amines compound of the present invention, in the manufacturing of the organic EL that has used this compound, can utilize film to come stackedization with the coating that forms solution, can carry out the wet type film forming, use the organic EL of this solution to present various luminous tones, thermotolerance height, if particularly aromatic amines compound of the present invention is injected, carries material as the hole, then hole injection, conveying property height, luminosity height and luminous efficiency height, the life-span is long.

Embodiment

Aromatic amines compound of the present invention is the aromatic amines compound of following general formula (1) expression.

[changing 12]

In the general formula (1), Ar ₁～Ar ₆Expression replaces or does not have the aryl of carbonatoms 6～40 in the ring of replacement or replace or do not have the heteroaryl of carbonatoms 3～40 in the ring of replacement independently respectively, also has Ar ₁And Ar ₂, and Ar ₅And Ar ₆Also can link by singly-bound respectively and form carbazyl, R ₁～R ₄Represent halogen atom, carboxyl, amino, hydroxyl respectively independently, replace or do not have the carbonatoms 1～40 of replacement alkyl, replace or do not have the carbonatoms 2～40 of replacement alkenyl, replace or do not have replacement carbonatoms 2～40 alkynyl or replace or do not have the alkoxyl group of the carbonatoms 1～40 of replacement, n, m, p and q are respectively 0～4 integer.

In general formula (1), as Ar ₁～Ar ₆Ring in the example of aryl of carbonatoms 6～40, can enumerate phenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, terphenyl, 3,5-phenylbenzene phenyl, 3,5-two (1-naphthyl) phenyl, 3,5-two (2-naphthyl) phenyl, 3,4-phenylbenzene phenyl, the pentapheneyl phenyl, 4-(2, the 2-diphenylacetylene) phenyl, 4-(1,2,2-triphenyl vinyl) phenyl, fluorenyl, the 1-naphthyl, the 2-naphthyl, 4-(1-naphthyl) phenyl, 4-(2-naphthyl) phenyl, 3-(1-naphthyl) phenyl, 3-(2-naphthyl) phenyl, the 9-anthryl, the 2-anthryl, the 9-phenanthryl, the 1-pyrenyl, Qu Ji, naphthacenyl, section sieve (コロニ Le) base etc.

In general formula (1), as Ar ₁～Ar ₆Ring in the example of heteroaryl of carbonatoms 3～40; can enumerate the 1-pyrryl; the 2-pyrryl; the 3-pyrryl; pyrazinyl; pirimidyl; piridazyl; 2-pyrimidine (pyridinyl) base; the 3-pyrimidyl; the 4-pyrimidyl; the 1-indyl; the 2-indyl; the 3-indyl; the 4-indyl; the 5-indyl; the 6-indyl; the 7-indyl; the different nitrogen of 1-(mixing) indenyl; the different nitrogen of 2-(mixing) indenyl; the different nitrogen of 3-(mixing) indenyl; the different nitrogen of 4-(mixing) indenyl; the different nitrogen of 5-(mixing) indenyl; the different nitrogen of 6-(mixing) indenyl; the different nitrogen of 7-(mixing) indenyl; the 2-furyl; the 3-furyl; the 2-benzofuryl; the 3-benzofuryl; the 4-benzofuryl; the 5-benzofuryl; the 6-benzofuryl; the 7-benzofuryl; the 1-isobenzofuran-base; the 3-isobenzofuran-base; the 4-isobenzofuran-base; the 5-isobenzofuran-base; the 6-isobenzofuran-base; the 7-isobenzofuran-base; quinolyl; the 3-quinolyl; the 4-quinolyl; the 5-quinolyl; the 6-quinolyl; the 7-quinolyl; the 8-quinolyl; the 1-isoquinolyl; the 3-isoquinolyl; the 4-isoquinolyl; the 5-isoquinolyl; the 6-isoquinolyl; the 7-isoquinolyl; the 8-isoquinolyl; the 2-quinoxalinyl; the 5-quinoxalinyl; the 6-quinoxalinyl; the 1-phenanthridinyl; the 2-phenanthridinyl; the 3-phenanthridinyl; the 4-phenanthridinyl; the 6-phenanthridinyl; the 7-phenanthridinyl; the 8-phenanthridinyl; the 9-phenanthridinyl; the 10-phenanthridinyl; 1-acridine (acridinyl) base; the 2-acridyl; the 3-acridyl; the 4-acridyl; the 9-acridyl; 1; 7-phenanthrolene-2-acyl group; 1; 7-phenanthrolene-3-acyl group; 1; 7-phenanthrolene-4-acyl group; 1; 7-phenanthrolene-5-acyl group; 1; 7-phenanthrolene-6-acyl group; 1; 7-phenanthrolene-8-acyl group; 1; 7-phenanthrolene-9-acyl group; 1; 7-phenanthrolene-10-acyl group; 1; 8-phenanthrolene-2-acyl group; 1; 8-phenanthrolene-3-acyl group; 1; 8-phenanthrolene-4-acyl group; 1; 8-phenanthrolene-5-acyl group; 1; 8-phenanthrolene-6-acyl group; 1; 8-phenanthrolene-7-acyl group; 1; 8-phenanthrolene-9-acyl group; 1; 8-phenanthrolene-10-acyl group; 1; 9-phenanthrolene-2-acyl group; 1; 9-phenanthrolene-3-acyl group; 1; 9-phenanthrolene-4-acyl group; 1; 9-phenanthrolene-5-acyl group; 1; 9-phenanthrolene-6-acyl group; 1; 9-phenanthrolene-7-acyl group; 1; 9-phenanthrolene-8-acyl group; 1; 9-phenanthrolene-10-acyl group; 1; 10-phenanthrolene-2-acyl group; 1; 10-phenanthrolene-3-acyl group; 1; 10-phenanthrolene-4-acyl group; 1; 10-phenanthrolene-5-acyl group; 2; 9-phenanthrolene-1-acyl group; 2; 9-phenanthrolene-3-acyl group; 2; 9-phenanthrolene-4-acyl group; 2; 9-phenanthrolene-5-acyl group; 2; 9-phenanthrolene-6-acyl group; 2; 9-phenanthrolene-7-acyl group; 2; 9-phenanthrolene-8-acyl group; 2; 9-phenanthrolene-10-acyl group; 2; 8-phenanthrolene-1-acyl group; 2; 8-phenanthrolene-3-acyl group; 2; 8-phenanthrolene-4-acyl group; 2; 8-phenanthrolene-5-acyl group; 2; 8-phenanthrolene-6-acyl group; 2; 8-phenanthrolene-7-acyl group; 2; 8-phenanthrolene-9-acyl group; 2; 8-phenanthrolene-10-acyl group; 2; 7-phenanthrolene-1-acyl group; 2; 7-phenanthrolene-3-acyl group; 2; 7-phenanthrolene-4-acyl group; 2; 7-phenanthrolene-5-acyl group; 2; 7-phenanthrolene-6-acyl group; 2; 7-phenanthrolene-8-acyl group; 2; 7-phenanthrolene-9-acyl group; 2,7-phenanthrolene-10-acyl group; the 1-phenazinyl; the 2-phenazinyl; the 1-phenothiazinyl; the 2-phenothiazinyl; the 3-phenothiazinyl; the 4-phenothiazinyl; the lysivane base; the 1-phenoxazinyl; the 2-phenoxazinyl; the 3-phenoxazinyl; the 4-phenoxazinyl; the 10-phenoxazinyl; 2-oxazole (oxazolyl) base; the 4-oxazolyl; the 5-oxazolyl; 2-oxadiazole (oxadiazolyl) base; 5-oxadiazole base; 3-furan a word used for translation (furazanyl) base; the 2-thienyl; the 3-thienyl; 2-methylpyrrole-1-acyl group; 2-methylpyrrole-3-acyl group; 2-methylpyrrole-4-acyl group; 2-methylpyrrole-5-acyl group; 3-methylpyrrole-1-acyl group; 3-methylpyrrole-2-acyl group; 3-methylpyrrole-4-acyl group; 3-methylpyrrole-5-acyl group; 2-tertiary butyl pyrroles-4-acyl group; 3-(2-phenyl propyl) pyrroles-1-acyl group; 2-methyl isophthalic acid-indyl; 4-methyl isophthalic acid-indyl; 2-methyl-3-indyl; 4-methyl-3-indyl; the 2-tertiary butyl-1-indyl; the 4-tertiary butyl-1-indyl; the 2-tertiary butyl-3-indyl; the 4-tertiary butyl-3-indyl etc.

In general formula (1), substituent R ₁～R ₄Halogen atom can enumerate fluorine, chlorine, bromine, iodine and astatine.

In general formula (1), as substituent R ₁～R ₄Replacement or do not have the example of alkyl of the carbonatoms 1～50 of replacement, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2,3-dihydroxyl-tertiary butyl, 1,2,3-trihydroxy-propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-two bromo-tertiary butyls, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-two iodo-tertiary butyls, 1,2,3-triiodo propyl group, amino methyl, the 1-aminoethyl, the 2-aminoethyl, 2-aminoisobutyric base, 1, the 2-diaminoethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl, 1,2,3-triamino propyl group, cyano methyl, the 1-cyano methyl, the 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2,3-dicyano-tertiary butyl, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2,3-dinitrobenzene-tertiary butyl, 1,2,3-trinitro-propyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, the 4-methylcyclohexyl, 1-diamantane (adamantyl) base, the 2-adamantyl, 1-norborneol (norbornyl) base, 2-norcamphyl etc.

In general formula (1), as substituent R ₁～R ₄Replacement or do not have the example of alkenyl of the carbonatoms 2～40 of replacement, can enumerate vinyl, allyl group, 1-butylene base, crotyl, 3-butenyl, 1,3-butadienyl, 1-methyl ethylene, styryl, 2,2-diphenylacetylene, 1,2-diphenylacetylene, 1-methacrylic, 1,1-dimethyl-allyl, 2-methacrylic, 1-phenyl allyl group, 2-phenyl allyl group, 3-phenyl allyl group, 3,3-phenylbenzene allyl group, 1,2-dimethyl-allyl, 1-phenyl-1-butylene base, 3-phenyl-1-butylene base etc.

In general formula (1), as substituent R ₁～R ₄Replacement or do not have the example of alkynyl of the carbonatoms 2～40 of replacement, can enumerate ethynyl, propargyl, 3-pentynyl etc.

In general formula (1), as substituent R ₁～R ₄Replacement or do not have the example of alkoxyl group of the carbonatoms 1～50 of replacement, can enumerate-OY ₁The base of expression is as Y ₁Example, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dicyano sec.-propyl, 2,3-dihydroxyl-tertiary butyl, 1,2,3-three hydroxypropyls, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2, the 3-Dichloroethyl, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-two bromo-tertiary butyls, 1,2,3-three bromopropyls, iodomethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-two bromo-tertiary butyls, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-two iodo-tertiary butyls, 1,2,3-triiodo propyl group, amino methyl, the 1-aminoethyl, the 2-aminoethyl, 2-aminoisobutyric base, 1, the 2-diaminoethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl, 1,2,3-triamino propyl group, cyano methyl, the 1-cyano methyl, the 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2,3-dicyano-tertiary butyl, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2,3-dinitrobenzene-tertiary butyl, 1,2,3-trinitro-propyl group etc.

In described general formula (1), L is the divalent concatenating group with following general formula (2) and (3) expression,

-(Ar ₇) _n-(Ar ₈) _b-(Ar ₉) _c- (2)

[changing 13]

The preferred concrete example of the aromatic amines compound of general formula of the present invention (1) expression is as described below, but is not limited to these exemplary compounds.

[changing 14]

[changing 15]

[changing 16]

Aromatic amines compound of the present invention is preferably the organic EL material, is particularly suitable for organic EL with hole transporting material or hole-injecting material.One deck at least of the liquid crystal film layer of organic EL of the present invention contains described aromatic amines compound.Described aromatic amines compound especially preferably is contained in cavity conveying zone or hole injection zone, and then is preferably main component.In cavity conveying zone or hole injection zone, contain described aromatic amines compound, thus and then preferred wet type film forming luminescent layer making organic EL.In addition, the present invention also provides a kind of organic EL that contains more than the described aromatic amines compound 0.1 quality % to use with film and forms solution.

Below the component structure of organic EL of the present invention is described.

(1) structure of organic EL

As the representative elements structure of organic EL of the present invention, can enumerate

(1) anode/luminescent layer/negative electrode

(2) anode/hole injection layer/luminescent layer/negative electrode

(3) anode/luminescent layer/electron injecting layer/negative electrode

(4) anode/hole injection layer/luminescent layer/electron injecting layer/negative electrode

(5) anode/organic semiconductor layer/luminescent layer/negative electrode

(6) anode/organic semiconductor layer/electronic barrier layer/luminescent layer/negative electrode

(7) anode/organic semiconductor layer/luminescent layer/adhere to improves layer/negative electrode

(8) anode/hole injection layer/hole transporting layer/luminescent layer/electron injecting layer/negative electrode

(9) anode/insulation layer/luminescent layer/insulation layer/negative electrode

(10) anode/electrodeless semiconductor layer/insulation layer/luminescent layer/insulation layer/negative electrode

(11) anode/organic semiconductor layer/insulation layer/luminescent layer/insulation layer/negative electrode

(12) anode/insulation layer/hole injection layer/hole transporting layer/luminescent layer/insulation layer/negative electrode

(13) anode/insulation layer/hole injection layer/hole transporting layer/luminescent layer/electron injecting layer/structures such as negative electrode.

Wherein, the preferred usually structure of using (8), but be not limited to this.

Aromatic amine derivative of the present invention also can be used for the liquid crystal film layer of organic EL etc., also can be used for light-emitting zone or cavity conveying zone, preferably by being used for the cavity conveying zone, being particularly preferred for hole transporting layer, thereby molecule is difficult to take place crystallization, improves the yield rate when making organic EL.

The amount that aromatic amine derivative of the present invention contains in the liquid crystal film layer is preferably 30～100mol%.

(2) light-transmitting substrate

On the substrate of light transmission, make organic EL substrate of the present invention.Light-transmitting substrate described herein is the substrate that supports organic EL, preferably in the transmitance of the visibility region light of 400～700nm is more than 50%, level and smooth substrate.

Particularly, can enumerate sheet glass, polymer sheet.As sheet glass, especially can enumerate soda-lime glass, contain barium strontium glass, lead glass, aluminum silicate glass, pyrex, barium borosilicate glass, quartz etc.In addition, as polymer sheet, can enumerate polycarbonate, vinylformic acid, polyethylene terephthalate, polyether sulfides, polysulfones etc.

(3) anode

The anode of organic EL of the present invention has the function to hole transporting layer or luminescent layer injected hole, has the above work function of 4.5eV, and is very effective.As the concrete example of the anode material that uses among the present invention, can enumerate tin indium oxide alloy (ITO), stannic oxide (NESA), indium-zinc oxide (IZO), gold and silver, platinum, copper etc.

Anode can make these electrode substance film forming by utilizing methods such as sedimentation or sputtering method.

Taking out from anode like this under the luminous situation of spontaneous photosphere, the luminous relatively transmitance of preferred anodes is greater than 10%.In addition, the anodic sheet resistance is preferably below hundreds of Ω/.The anodic thickness is according to material and difference, usually from 10nm～1 μ m, preferably select from the scope of 10～200nm.

(4) luminescent layer

The luminescent layer of organic EL has the function of following (1)～(3) simultaneously.

(1) function of injecting; Can be when applying electric field from anode or hole injection layer injected hole, can inject the function of electronics from negative electrode or electron injecting layer

(2) conveying function; The function that the electric charge (electronics and hole) that injected is moved in the power of electric field

(3) lighting function; The place of bonded again in electronics and hole is provided, it is related to luminous function

Wherein, even the easy degree of injection of easy degree of the injection in hole and electronics there are differences, perhaps can there be size in the conveying of showing with hole and movement of electrons kilsyth basalt, but the electric charge of preferred mobile any one party.

Method as forming this luminescent layer for example can be suitable for known method such as sedimentation, spin-coating method, LB method.Luminescent layer is preferably the packing of molecules film especially.Be meant the film that forms from the material compound deposit coating of gas phase state or the film that forms from the material compound solidification of solution state or liquid phase state at this packing of molecules film, usually this packing of molecules film is different with the film (molecule built-up film) that forms with the LB method, can utilize different or its function difference that causes of aggregated structure, higher order structure to distinguish.

In addition, open in the clear 57-51781 communique as the spy disclosed, also can tackiness agents such as resin and material compound are dissolved in become solution in the solvent after, utilize spin-coating method etc. with its filming, form luminescent layer.

In the present invention, in the scope of not destroying the object of the invention, also can in luminescent layer, contain luminescent material other the known luminescent materials in addition that constitute by aromatic amine derivative of the present invention as required, in addition, also can be on the luminescent layer that contains the luminescent material that constitutes by aromatic amine derivative of the present invention the stacked luminescent layer that contains other known luminescent materials.

As the luminescent material or the dopant material that can in luminescent layer, use with aromatic amine derivative of the present invention, for example can enumerate anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene,

(chrysene), fluorescein perylene, naphthalene perylene (Na Off ロペリレ Application, naphthaloperylene), purple cyclic ketones (ペリノ Application, perynone), phthalein and week are because of ketone, purple cyclic ketones (the Na Off ロペリノ Application of naphthalene, naphthaloperinone), diphenyl diethylene, tetraphenylbutadiene, tonka bean camphor oxadiazole, aldazine, dibenzoxazine quinoline (bisbenzoxazoline), bisstyryl, pyrazine, cyclopentadiene, the quinoline metal complex, the quinolylamine metal complex, the benzoquinoline metal complex, imines, toluylene, vinyl anthracene, the diamino carbazole, pyrans, thiapyran, polymethine, merocyanine, imidazoles chelating oxine ketone (oxinoid) compound, quinoline a word used for translation (two) ketone, rubrene and fluorochrome etc., but be not limited to these.

As the substrate material that in luminescent layer, uses with aromatic amine derivative of the present invention, the compound of preferably following (i)～(ix) expression.

The asymmetric anthracene of following general formula (i) expression.

[changing 17]

(in the formula, Ar is the condensation aromatic series base of carbonatoms 10～50 in replacement or the ring that does not have replacement.

Ar ' is the aromatic series base of carbonatoms 6～50 in replacement or the ring that does not have replacement.

X is the aromatic series base of carbonatoms 6～50 in replacement or the ring that does not have replacement, replace or do not have the aromatic heterocycle of the member 5～50 of replacement, replace or do not have the alkyl of the carbonatoms 1～50 of replacement, replace or do not have the alkoxyl group of the carbonatoms 1～50 of replacement, replace or do not have the aralkyl of the carbonatoms 6～50 of replacement, replace or do not have the aryloxy of the member 5～50 of replacement, replace or do not have the aryl thio group of the member 5～50 of replacement, replace or do not have the alkoxy carbonyl of the carbonatoms 1～50 of replacement, carboxyl, halogen atom, cyano group, nitro, hydroxyl.

A, b and c are respectively 0～4 integer.

N is 1～3 integer.In addition, n is under the situation more than 2, and is identical or different in [].)

The asymmetric Monoanthracene derivative that following general formula is (ii) represented.

[changing 18]

(in the formula, Ar ¹And Ar ²Expression replaces or does not have the aromatic series cyclic group of carbonatoms 6～50 in the ring of replacement independently respectively, and m and n are respectively 1～4 integer.Wherein, at m=n=1 and Ar ¹With Ar ²Under the symmetrical situation of the binding site of phenyl ring, there is not Ar ¹With Ar ²The base that inequality or relative X-Y axle becomes symmetric form is incorporated into 1～8 situation of anthracene nucleus.M or n are that m is different integers with n under the situation of 2～4 integer.

R ¹～R ¹⁰Represent hydrogen atom respectively independently, replace or do not have the aromatic series cyclic group of carbonatoms 6～50 in the ring of replacement, replace or do not have the aromatic heterocycle of carbonatoms 5～50 in the ring of replacement, replace or do not have the alkyl of the carbonatoms 1～50 of replacement, replace or do not have the cyclohexyl of replacement, replace or do not have the alkoxyl group of the carbonatoms 1～50 of replacement, replace or do not have the aralkyl of the carbonatoms 6～50 of replacement, replace or do not have the aryloxy of the member 5～50 of replacement, replace or do not have the aryl thio group of the member 5～50 of replacement, replace or do not have the alkoxy carbonyl of the carbonatoms 1～50 of replacement, replace or do not have the silyl of replacement, carboxyl, halogen atom, cyano group, nitro, hydroxyl.)

The asymmetric pyrene derivatives that following general formula is (iii) represented.

[changing 19]

[in the formula, Ar and Ar ' represent to replace or do not have the aromatic series base of carbonatoms 6～50 in the ring of replacement independently of one another.

L and L ' represent independently of one another to replace or do not have replacement phenylene, replace or do not have replacement naphthalene alkene (Na Off レニレ Application, naphthalenylene) base, replace or do not have inferior fluorenes (the Off Le オレニレ Application) base of replacement or replace or do not have inferior fluorenes (the ジベ Application ヅシロリレ Application) base of dibenzo of replacement.

M is 0～2 integer, and n is 1～4 integer, and s is 0～2 integer, and t is 0～4 integer.

In addition, L or Ar are incorporated into any one of 1～5 of pyrene, and L ' or Ar ' are incorporated into any one of 6～10 of pyrene.

Wherein, when n+t was even number, Ar, Ar ', L, L ' satisfied following (1) or (2).

(1) Ar ≠ Ar ' and/or L ≠ L ' (at this, ≠ be expressed as the base of different structure.)

(2) when Ar=Ar ' and L=L ',

(2-1) m ≠ s and/or n ≠ t, perhaps

(2-2) when m=s and n=t,

(2-2-1) L and L ' or pyrene be incorporated into respectively on Ar and the Ar ' different binding sites or (2-2-2) L and L ' or pyrene be incorporated under the situation of the identical combination position on Ar and the Ar ', not having L and L ' or Ar and Ar ' the position of substitution in pyrene is 1 and 6 or 2 and 7 s' situation.]

The asymmetric anthracene derivant that following general formula is (iv) represented.

[changing 20]

(in the formula, A ¹And A ²Expression replaces or does not have the condensation aromatic series cyclic group of carbonatoms 10～20 in the ring of replacement independently of one another.

Ar ¹And Ar ²Represent hydrogen atom or replacement independently of one another or do not have the aromatic series cyclic group of carbonatoms 6～50 in the ring of replacement.

Ar ¹, Ar ², R ⁹And R ¹⁰Can be respectively a plurality of, also can between adjacent group, form saturated or undersaturated ring texture.

Wherein, in the general formula (1), on 9 and 10 of the anthracene at center, do not become the situation of the group of symmetric form in conjunction with the X-Y axle shown in relatively on this anthracene.)

Following general formula (v) Biao Shi anthracene derivant.

[changing 21]

(in the formula, R ¹～R ¹⁰Represent hydrogen atom, alkyl, cycloalkyl, commutable aryl, alkoxyl group, aryloxy, alkylamino, alkenyl, arylamino or commutable hetero ring type base independently of one another, a and b represent 1～5 integer respectively, and they are under the situation more than 2, R ¹Between or R ²Between respectively identical or different, in addition, R ¹Between or R ²Between also can in conjunction with and form ring, R ³With R ⁴, R ⁵With R ⁶, R ⁷With R ⁸, R ⁹With R ¹⁰Also can be bonded to each other and form ring.L ¹The expression singly-bound ,-O-,-S-,-N (R)-(R is alkyl or commutable aryl), alkylidene group or arylalkenyl.)

Following general formula (vi) Biao Shi anthracene derivant.

[changing 22]

(in the formula, R ¹¹～R ²⁰Represent hydrogen atom, alkyl, cycloalkyl, aryl, alkoxyl group, aryloxy, alkylamino, arylamino or commutable hetero ring type base independently of one another, c, d, e and f represent 1～5 integer respectively, and they are under the situation more than 2, R ¹¹Between, R ¹²Between, R ¹⁶Between or R ¹⁷Between respectively identical or different, in addition, R ¹¹Between, R ¹²Between, R ¹⁶Between or R ¹⁷Between also can in conjunction with and form ring, R ¹³With R ¹⁴, R ¹⁸With R ¹⁹Also can be bonded to each other and form ring.L ²The expression singly-bound ,-O-,-S-,-N (R)-(R is alkyl or commutable aryl), alkylidene group or arylalkenyl.)

Following general formula (vii) Biao Shi spirofluorene derivative.

[changing 23]

(in the formula, A ⁵～A ⁸Expression replaces or does not have the xenyl or the replacement of replacement or do not have the naphthyl of replacement independently of one another.)

(viii) expression contains the condensation and cyclization compound to following general formula.

[changing 24]

(in the formula, A ⁹～A ¹⁴Same as described above, R ²¹～R ²³Represent arylamino, nitro, the cyano group of aralkoxy, the carbonatoms 5～16 of aryloxy, the carbonatoms 7～18 of alkoxyl group, the carbonatoms 5～18 of cycloalkyl, the carbonatoms 1～6 of alkyl, the carbonatoms 3～6 of hydrogen atom, carbonatoms 1～6, the ester group or the halogen atom of carbonatoms 1～6 independently of one another, A ⁹～A ¹⁴In at least one be group with the above condensation aromatic ring of 3 rings.)

The fluorene compound of following general formula (ix) expression.

[changing 25]

(in the formula, R ₁And R ₂Expression hydrogen atom, the alkyl that replaces or do not have replacement, the aralkyl that replaces or do not have replacement, the aryl that replaces or do not have replacement, the heterocyclic radical that replaces or do not have replacement, substituted-amino, cyano group or halogen atom.Be incorporated into the R of different fluorenyls ₁Between, R ₂Between identical or different, be incorporated into the R of identical fluorenyl ₁And R ₂Identical or different.R ₃And R ₄The expression hydrogen atom, replace or do not have replacement alkyl, replace or do not have replacement aralkyl, replace or do not have the aryl or the replacement of replacement or do not have the heterocyclic radical of replacement, be incorporated into the R of different fluorenyls ₃Between, R ₄Between identical or different, be incorporated into the R of identical fluorenyl ₃And R ₄Identical or different.Ar ₁And Ar ₂The ading up to the replacement more than 3 or do not have the fused-ring aromatic base of replacement or phenyl ring and heterocyclic add up to and be incorporated into the condensation polycyclic heterocyclic radical of fluorenyl, Ar with replacement or the carbon that do not have a replacement more than 3 of expression phenyl ring ₁And Ar ₂Identical or different.N represents 1～10 integer.)

In above substrate material, preferred anthracene derivant and then preferred Monoanthracene derivative, preferred especially asymmetric anthracene.

In addition, as the luminescent material of doping agent, also can use the luminiferous compound of phosphorescence.As the luminiferous compound of phosphorescence, preferably in substrate material, contain the compound of carbazole ring.As doping agent, for can be from the luminous compound of triple excitons, as long as it is luminous from triple excitons, be not particularly limited, be preferably the metal complex that contains at least a metal of selecting from the group that Ir, Ru, Pd, Pt, Os and Re constitute, preferred porphyrin metal coordination compound or adjacent methyl (オ Le トメ Le) are changed metal complex.

Contain the luminous institute of phosphorescence that the compound of carbazole ring constitutes preferably matrix be to have the compound that the result who moves to phosphorescence luminance compound generation energy from its excited state makes the luminous function of phosphorescence luminance compound.As matrix compounds, so long as the exciton energy can be got final product to the compound that phosphorescence luminance compound energy moves, be not particularly limited, can suitably select according to purpose.Except the carbazole ring, can also have any heterocycle etc.

As the concrete example of such matrix compounds, can enumerate carbazole derivative, triazole derivative oxazole derivative oxadiazole derivative, imdazole derivatives, poly-aryl chain alkane derivatives, pyrazoline derivative, the pyrazolone derivative, phenylenediamine derivative, aryl amine derivatives, the amino chalcone derivative that replaces, the styryl anthracene derivant, fluorenone derivatives, hydrazine derivative, stilbene derivatives, the silazane derivative, aromatic uncle amine compound, the styrylamine compound, aromatic series dimethylene (dimethylidene) based compound, the porphyrin based compound, anthraquinone bismethane (anthraquinodimathane) derivative, anthracyclinone derivatives, the diphenyl benzene quinone derivative, the thiapyran dioxide derivative, carbodiimide derivative, the fluorenylidene methane Derivatives, the diphenylethyllene pyrazines derivatives, heterocycle tetracarboxylic anhydrides such as naphthalene perylene, the phthalocyanine pigment derivative, the metal complex of oxine derivative or metal phthalocyanine dyestuff, being the various metal complex polysilane based compounds of representative as the metal complex of dentate with benzoxazole or benzothiazole, poly-(N-vinylcarbazole) derivative, the aniline based copolymer, the thiophene oligomer, electroconductive polymer oligomers such as Polythiophene, polythiofuran derivative, the polyphenylene derivative, the polyphenylene vinylene derivative, macromolecular compounds such as poly-fluorene derivatives etc.Matrix compounds can use separately, also can be also with two or more.

As concrete example, can enumerate compound as described below.

[changing 26]

The luminiferous doping agent of phosphorescence is can be from the luminous compound of triple excitons.As long as it is luminous from triple excitons, be not particularly limited, be preferably the metal complex that contains at least a metal of from the group that Ir, Ru, Pd, Pt, Os and Re constitute, selecting, preferred porphyrin metal coordination compound or ortho-metalated (Ortho Metalation オ Le トメ Le) metal complex.As the porphyrin metal coordination compound, preferred porphyrin iridium-platinum complex.The phosphorescence luminance compound can use separately, also can be also with two or more.

The dentate that the ortho-metalated metal complex of various formation is arranged, preferred 2-phenylpyridine derivative, 7,8-benzoquinoline derivative, 2-(2-thienyl) pyridine derivate, 2-(1-naphthyl) pyridine derivate, 2-phenylquinoline derivative etc.These derivatives also can have substituting group as required.The compound of fluorochemical, importing trifluoromethyl is a doping agent as blueness especially preferably.And then, also can have above-mentioned dentates such as methyl ethyl diketone dentate, picric acid dentate in addition as auxiliary dentate.

As the content of the luminiferous doping agent of phosphorescence in luminescent layer, be not particularly limited, can suitably select according to purpose, for example be 0.1～70 quality %, be preferably 1～30 quality %.If the content of phosphorescence luminance compound is then luminous faint less than 0.1 quality %, can not bring into play it fully and contain and produce effect, surpass 70 quality % then, the phenomenon that then is called as the concentration delustring becomes significantly, the element function reduction.

In addition, luminescent layer also can contain hole transporting material, electron transport materials, polymer binder as required.

And then the thickness of luminescent layer is preferably 5～50nm, and more preferably 7～50nm most preferably is 10～50nm.If less than 5nm, then be difficult to form luminescent layer, it is difficult that the adjustment of colourity may become, if surpass 50nm, then driving voltage may rise.

(5) transfer layer (cavity conveying zone) is injected in the hole

It is to help to the luminescent layer injected hole and be transported to the layer of light-emitting zone that transfer layer is injected in the hole, and the hole degree of excursion is big, and the ionization energy is little to 5.5eV usually.Inject transfer layer as such hole, preferably carry the material in hole to luminescent layer, and then the degree of excursion in hole is for example applying 10 with lower strength of electric field ⁴～10 ⁶During the electric field of V/cm, be preferably 10 at least ^-4Cm ²/ V second.

Aromatic amine derivative of the present invention is being used under the situation in cavity conveying zone, can forming hole injection, transfer layer separately, also can mix use with other materials with aromatic amine derivative of the present invention.

As forming the material that transfer layer is injected in the hole with aromatic amine derivative activation of the present invention, get final product so long as have the material of described preferred character, be not particularly limited, can select to use in the past in light-guide material as the charge transport material in hole and habitual material, perhaps inject any materials of the material known that transfer layer uses in the hole of organic EL.

As concrete example, can enumerate triazole derivative (with reference to United States Patent (USP) 3,112, No. 197 specification sheetss etc.) oxadiazole derivative is (with reference to United States Patent (USP) 3,189, No. 447 specification sheetss etc.), imdazole derivatives (the special public clear 37-16096 communique of reference etc.), poly-aryl chain alkane derivatives is (with reference to United States Patent (USP) 3,615, No. 402 specification sheetss, United States Patent (USP) the 3rd, 820, No. 989 specification sheetss, United States Patent (USP) the 3rd, 542, No. 544 specification sheetss, special public clear 45-555 communique, special public clear 51-10983 communique, the spy opens clear 5 1-93224 communiques, the spy opens clear 55-17105 communique, the spy opens clear 56-4148 communique, the spy opens clear 55-108667 communique, the spy opens clear 55-156953 communique, the spy opens clear 56-36656 communique etc.), pyrazoline derivative and pyrazolone derivative are (with reference to United States Patent (USP) the 3rd, 180, No. 729 specification sheetss, United States Patent (USP) the 4th, 278, No. 746 specification sheetss, the spy opens clear 55-88064 communique, the spy opens clear 55-88065 communique, the spy opens clear 49-105537 communique, the spy opens clear 55-51086 communique, the spy opens clear 56-80051 communique, the spy opens clear 56-88141 communique, the spy opens clear 57-45545 communique, the spy opens clear 54-112637 communique, the spy opens clear 55-74546 communique etc.), phenylenediamine derivative is (with reference to United States Patent (USP) the 3rd, 615, No. 404 specification sheetss, special public clear 51-10105 communique, special public clear 46-3712 communique, special public clear 47-25336 communique, the spy opens clear 54-53435 communique, the spy opens clear 54-110536 communique, the spy opens clear 54-119925 communique etc.), aryl amine derivatives is (with reference to United States Patent (USP) the 3rd, 567, No. 450 specification sheetss, United States Patent (USP) the 3rd, 180, No. 703 specification sheetss, United States Patent (USP) the 4th, 175, No. 961 specification sheetss, United States Patent (USP) the 4th, 012, No. 376 specification sheetss, special public clear 49-35702 communique, special public clear 39-27577 communique, the spy opens clear 55-144250 communique, the spy opens clear 56-119132 communique, the spy opens clear 56-22437 communique, Deutsches Reichs-Patent the 1st, 110, No. 518 specification sheetss etc.), the amino chalcone derivative that replaces is (with reference to United States Patent (USP) the 3rd, 526, No. 501 specification sheetss etc.) oxazole derivative is (at United States Patent (USP) the 3rd, 257, disclosed in No. 203 specification sheetss etc.), styryl anthracene derivant (opening clear 56-46234 communique etc. with reference to the spy), fluorenone derivatives (opening clear 54-110837 communique etc. with reference to the spy), hydrazine derivative is (with reference to United States Patent (USP) the 3rd, 717, No. 462 specification sheetss, the spy opens clear 54-59143 communique, the spy opens clear 55-52063 communique, the spy opens clear 55-52064 communique, the spy opens clear 55-46760 communique, the spy opens clear 55-85495 communique, the spy opens clear 57-11350 communique, the spy opens clear 57-148749 communique, Te Kaiping 2-311591 communique etc.), stilbene derivatives (is opened clear 61-210363 communique with reference to the spy, the spy opens clear 61-228451 communique, the spy opens clear 61-14642 communique, the spy opens clear 61-72255 communique, the spy opens clear 62-47646 communique, the spy opens clear 62-36674 communique, the spy opens clear 62-10652 communique, the spy opens clear 62-30255 communique, the spy opens clear 60-93455 communique, the spy opens clear 60-94462 communique, the spy opens clear 60-174749 communique, the spy opens clear 60-175052 communique etc.), silazane derivative (United States Patent (USP) the 4th, 950, No. 950 specification sheetss), polysilane system (spy opens flat 2-204996 communique), aniline based copolymer (spy opens flat 2-282263 communique), disclosed electroconductive polymer oligomer in the Te Kaiping 1-211399 communique (particularly thiophene oligomer) etc.

The material that injects transfer layer as the hole can use above-mentioned materials, the preferred porphyrin compound (opening in the clear 63-2956965 communique etc. disclosed) that uses the spy, aromatic series uncle ammoniate and styrylamine compound are (with reference to United States Patent (USP) the 4th, 127, No. 412 specification sheetss, the spy opens clear 53-27033 specification sheets, the spy opens clear 54-58445 communique, the spy opens clear 54-149634 communique, the spy opens clear 54-64299 communique, the spy opens clear 55-79450 communique, the spy opens clear 55-144250 communique, the spy opens clear 56-119132 communique, the spy opens clear 61-295558 communique, the spy opens clear 61-98353 communique, the spy opens clear 63-295605 communique etc.), especially preferably use aromatic uncle amine compound.

In addition, can also enumerate United States Patent (USP) the 5th, 061, record has for example 4 of 2 condensation aromatic rings at intramolecularly in No. 569,4 '-two (N-(1-naphthyl)-N-phenyl amino) two phenyl (being designated hereinafter simply as NPD), perhaps special open the triphenylamine unit of putting down in writing in the flat 4-308688 communique be joined into 3 star bursts (star burst) type 4,4 ', 4 "-three (N-(3-aminomethyl phenyl)-N-anilino) triphenylamine (being designated hereinafter simply as MTDATA) etc.

And then except as described aromatic series dimethylene (dimethylidene) based compound shown in the material of luminescent layer, mineral compound such as p type Si, p type SiC also can inject the material of transfer layer as the hole.

Transfer layer can known method filming aromatic amine derivatives of the present invention such as vacuum deposition method, spin-coating method, teeming practice, LB method form by for example utilizing in the hole injection.The thickness that injects transfer layer as the hole is not particularly limited, and is generally 5nm～5 μ m.Transfer layer is injected as long as contain aromatic amine derivative of the present invention in the cavity conveying zone in this hole, can use one deck of one or more formations of above-mentioned materials to constitute, also can inject the hole injection transfer layer that other different compounds of transfer layer constitute in stacked and described hole.

In addition, the layer as helping to luminescent layer injected hole or injection electronics also can be provided with organic semiconductor layer, preferably has 10 ^-10The specific conductivity that S/cm is above.As the material of such organic semiconductor layer, can use to contain the thiophene oligomer or open disclosedly in the flat 8-193191 communique to contain electroconductibility oligomers such as arylamine oligomer, contain electroconductibility branch-shape polymer of arylamine branch-shape polymer (dendrimer) etc. etc. the spy.

(6) electronics injects transfer layer

Then the electron injecting layer transfer layer is to help to inject electronics, be delivered to the layer of light-emitting zone to luminescent layer, and the electron migration degree is big, in addition, adhere to improve layer be in this electron injecting layer with adhering to of the negative electrode layer that constitutes of good especially material.

In addition, the known because light that sends is by electrode (being negative electrode in this case) reflection, thus organic EL interfere directly from take out luminous of anode and take out via the reflection of electrode luminous.In order to effectively utilize this interference effect, suitably select electron supplying layer with the thickness of counting nm～number μ m, but thickness is when thick especially, rise and applying 10 for fear of voltage ⁴～10 ⁶The preferred electron degree of excursion is at least 10 during the electric field of V/cm ^-6Cm ²More than/the Vs.

As the material that uses in the electron injecting layer, the metal complex Huo person oxadiazole derivative of preferred oxine or derivatives thereof.Concrete example as the metal complex of described oxine or derivatives thereof, can use metallo-chelate oxine ketone (oxinoid) compound of the inner complex that contains oxine (oxine) (being generally 8-quinolinone or oxine), for example can use three (oxine) aluminium as the electronics injecting material.

On the other hand, Zuo Wei oxadiazole derivative can be enumerated the electron transport compound that following general formula is represented.

[changing 27]

(in the formula, Ar ¹, Ar ², Ar ³, Ar ⁵, Ar ⁶, Ar ⁹Expression replaces or does not have the aryl of replacement respectively, is same to each other or different to each other respectively.In addition, Ar ⁴, Ar ⁷, Ar ⁸Expression replaces or does not have the arylalkenyl of replacement respectively, is same to each other or different to each other respectively.)

At this, as aryl, can enumerate phenyl, xenyl, anthryl, piperidyl (ペリレニ Le, perylenyl), pyrenyl.In addition, as arylalkenyl, can enumerate phenylene, naphthylidene, biphenylene, anthrylene, piperidines alkene (perylenylene), pyrene thiazolinyl (ピレニレ Application, pyrenylene) etc.In addition, as substituting group, can enumerate the alkoxyl group of alkyl, carbonatoms 1～10 of carbonatoms 1～10 or cyano group etc.This electron transport compound is preferably the compound of film formation property.

[changing 28]

And then, as the material that uses in electron injecting layer and the electron supplying layer, also can use the material of following general formula (A)～(E) expression.

[changing 29]

(general formula (A) and (B) in, A ¹～A ³Represent nitrogen-atoms or carbon atom independently of one another.

Ar ¹Expression replaces or does not have the aryl or the replacement of carbonatoms 6～60 in the ring of replacement or do not have the heteroaryl of carbonatoms 3～60 in the ring of replacement, Ar ²The expression hydrogen atom, replace or do not have carbonatoms 6～60 in the ring of replacement aryl, replace or do not have carbonatoms 3～60 in the ring of replacement heteroaryl, replace or do not have replacement carbonatoms 1～20 alkyl or replacement or do not have the alkoxyl group of carbonatoms 1～20 of replacement or their divalent group.Wherein, Ar ¹And Ar ²Any one party represent to replace or do not have the condensation cyclic group or the replacement of carbonatoms 10～60 in the ring of replacement or do not have the assorted condensation cyclic group of list of carbonatoms 3～60 in the ring of replacement.

L ¹, L ²And L represent singly-bound independently of one another, replace or do not have carbonatoms 6～60 in the ring of replacement arylalkenyl, replace or do not have the impure aromatic ene base or the replacement of carbonatoms 3～60 in the ring of replacement or do not have inferior fluorenes (fluorenylene) base of replacement.

R represent hydrogen atom, replace or do not have carbonatoms 6～60 in the ring of replacement aryl, replace or do not have carbonatoms 3～60 in the ring of replacement heteroaryl, replace or do not have replacement carbonatoms 1～20 alkyl or replace or do not have the alkoxyl group of the carbonatoms 1～20 of replacement, n is 0～5 integer, n is under the situation more than 2, a plurality of R are identical or different, in addition, also can be between adjacent a plurality of R groups in conjunction with forming carbon-ring type aliphatics ring or carbon-ring type aromatic ring.) expression nitogen-contained heterocycle derivant.

HAr-L-Ar ¹-Ar ² (C)

(in the formula, HAr represents to have the nitrogen heterocyclic ring of substituent carbonatoms 3～40, the impure aromatic ene base that L represents singly-bound, can have the arylalkenyl of substituent carbonatoms 6～60, can have a substituent carbonatoms 3～60 maybe can have substituent inferior fluorenes (fluorenylene) base, Ar ¹Expression can have the divalent aromatic hydrocarbyl of substituent carbonatoms 6～60, Ar ²The aryl that expression can have a substituent carbonatoms 6～60 maybe can have the heteroaryl of substituent carbonatoms 3～60.) expression nitogen-contained heterocycle derivant.

[changing 30]

(in the formula, X and Y represent independently of one another carbonatoms 1～6 saturated or undersaturated alkyl, alkoxyl group, alkenyloxy, alkynyloxy group, hydroxyl, replace or do not have replacement aryl, replace or do not have the heterocycle of replacement or X combines the structure that forms saturated or undersaturated ring, R with Y ₁～R ₄Represent hydrogen independently of one another; halogen atom; replace or do not have the alkyl of the carbonatoms 1～6 of replacement; alkoxyl group; aryloxy; perfluoroalkyl; perfluoro alkoxy; amino; alkyl-carbonyl; aryl carbonyl; alkoxy carbonyl; aryloxycarbonyl; azo-group; alkyl carbonyl oxy; aryloxy carbonyl oxygen base; sulfinyl; alkylsulfonyl; the sulfane base; silyl; formamyl; aryl; heterocyclic radical; alkenyl; alkynyl; nitro; formyl radical; nitroso-group; methanoyl; isocyano-; the cyanic acid alkali; isocyanate group; thiocyanate groups; isocyanide sulfenyl or cyano group or under adjacent situation, replace or do not have the structure of the cyclic condensation of replacement.) expression silicon (シラ) cyclopentadiene derivant.

[changing 31]

(in the formula, R ₁～R ₈And Z ₂Represent hydrogen atom, saturated or undersaturated alkyl, aromatic series base, heterocyclic radical, substituted-amino, replacement boryl, alkoxyl group or aryloxy independently of one another, X, Y and Z ₁Represent saturated or undersaturated alkyl, aromatic series base, heterocyclic radical, substituted-amino, alkoxyl group or aryloxy independently of one another, Z ₁And Z ₂The substituting group formation condensed ring that also can be bonded to each other, n represents 1～3 integer, n is under the situation more than 2, Z ₁Also can be different.Wherein, do not comprise that n is 1, X, Y and R ₂Be methyl, R ₈Be hydrogen atom or replace the situation of boryl, and n is 3, Z ₁Situation for methyl.) expression borane derivative.

[changing 32]

[in the formula, Q ¹And Q ²The dentate of representing following general formula (G) expression independently of one another, L represent halogen atom, replace or do not have replacement alkyl, replace or do not have replacement cycloalkyl, replace or do not have replacement aryl, replace or do not have replacement heterocyclic radical ,-OR ¹(R ¹The expression hydrogen atom, replace or do not have replacement alkyl, replace or do not have replacement cycloalkyl, replace or do not have replacement aryl, replace or do not have the heterocyclic radical of replacement.) or-O-Ga-Q ³(Q ⁴) (Q ³And Q ⁴With Q ¹And Q ²Identical) expression dentate.]

[changing 33]

[in the formula, ring A ¹And A ²Expression can have 6 Yuans aryl rings structures of substituent condensation each other.]

This metal complex is strong as the character of n N-type semiconductorN, and the electronics injectability is big.And then, because the generate energy when forming coordination compound is also low,, also become big as the fluorescence quantum efficiency of luminescent material so the metal of the metal complex that forms and the associativity of dentate also become firmly.

Ring A as the dentate that forms general formula (G) ¹And A ²Substituent concrete example; can enumerate chlorine; bromine; iodine; the halogen atom of fluorine; methyl; ethyl; propyl group; butyl; sec-butyl; the tertiary butyl; amyl group; hexyl; heptyl; octyl group; stearyl-; replacements such as trichloromethyl or do not have the alkyl of replacement; phenyl; naphthyl; the 3-aminomethyl phenyl; the 3-p-methoxy-phenyl; the 3-fluorophenyl; 3-trichloromethyl phenyl; the 3-trifluoromethyl; replacements such as 3-nitrophenyl or do not have the aryl of replacement; methoxyl group; n-butoxy; tert.-butoxy; the trichlorine methoxyl group; trifluoro ethoxy; five fluorine propoxy-; 2; 2; 3; 3-tetrafluoro propoxy-; 1; 1; 1; 3; 3; 3-hexafluoro-2-propoxy-; replacements such as 6-(perfluor ethyl) hexyloxy or do not have the alkoxyl group of replacement; phenoxy group; p-nitrophenyl oxygen base; to tertiary butyl phenoxy group; the 3-fluorophenoxy; pentafluorophenyl group; replacements such as 3-4-trifluoromethylphenopendant or do not have the aryloxy of replacement; methylthio group; ethylmercapto group; uncle's butylthio; own sulfenyl; hot sulfenyl; replacements such as trifluoromethylthio or do not have the alkylthio of replacement; thiophenyl; the p-nitrophenyl sulfenyl; to the tert.-butylbenzene sulfenyl; 3-fluorobenzene sulfenyl; the penta fluoro benzene sulfenyl; replacements such as 3-trifluoromethyl thiophenyl or do not have the arylthio of replacement; cyano group; nitro; amino; methylamino; diethylin; ethylamino-; diethylin; the dipropyl amido; dibutyl amino; list or disubstituted amidos such as hexichol amido; two (acetoxyl methyl) amino; two (acetoxyl ethyl) amino; two (acetoxyl propyl group) amino; amide group such as two (acetoxyl butyl) amino; hydroxyl; siloxy-; acyl group; the methylamino formyl radical; formyl-dimethylamino; the ethylamino formyl radical; the diethylamino formyl radical; the propyl group formamyl; the butyl formamyl; formamyls such as phenyl amino formyl radical; the carboxylic acid group; sulfonic group; imide; the pentamethylene base; cycloalkyl such as cyclohexyl; phenyl; naphthyl; xenyl; anthryl; phenanthryl; fluorenyl; aryl such as pyrenyl, pyridine (pyridinyl) base; pyrazinyl; pyrimidyl; pyridazinyl; triazinyl; indolinyl; quinoline (quinolinyl) base; acridine (acridinyl) base; pyrrolidyl; the dioxanyl base; piperidyl (piperidinyl); the morpholidinyl base; piperazinyl (ピペラジニ Le piperazinyl); the triathinyl base; carbazyl; furyl (furanyl); thiophenyl oxazolyl (oxazolyl) oxadiazole base (oxadiazolyl) benzoxazolyl (benzoxazolyl); thiazolyl; thiadiazolyl group (thiadiazolyl); benzothiazolyl (benzothiazolyl); triazolyl; imidazolyl; benzimidazolyl-; heterocyclic radicals such as puranyl base etc.In addition, between the above substituting group also can so that in conjunction with forming 6 Yuans aryl rings or heterocycle.

The interface zone that the optimal way of organic EL of the present invention is included in the zone of conveying electronic or negative electrode and organic layer contains the element of reductibility doping agent.At this, the reductibility doping agent is defined as reducing the material of electron transport compound.Thereby, get final product so long as have the material of certain reductibility, can use various materials, at least a material of selecting the group that for example can preferably use the organic coordination compounds of organic coordination compounds, the rare earth metal of the oxide compound from basic metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, alkaline-earth metal, the halogenide of alkaline-earth metal, the oxide compound of rare earth metal or the halogenide of olefines metal, alkali-metal organic coordination compounds, alkaline-earth metal to constitute.

In addition, more specifically, as preferred reductibility doping agent, especially preferably can enumerate by Na (work function: 2.36eV), K (work function: 2.28eV), Rb (work function: 2.16eV) and Cs (work function: 1.95eV) at least a basic metal of selecting in the group of Gou Chenging or by Ca (work function: 2.9eV), Sr (work function: 2.0～2.5eV) and Ba (work function: 2.52eV) work function of at least a alkaline-earth metal of selecting in the group of Gou Chenging is the following reductibility doping agent of 2.9eV.Wherein, at least a basic metal of selecting in the group that the reductibility doping agent more preferably is made of K, Rb and Cs, and then preferred Rb or Cs, most preferably Cs.These alkali-metal reducing powers are high especially, and are more a small amount of by inject the territory interpolation to electronics, just can realize the raising or the long lifetime of light emission luminance.In addition, be reductibility doping agent below the 2.9eV as work function, also preferred these two or more alkali-metal combinations especially preferably contain the combination of Cs, for example the combination of Cs and Na, Cs and K, Cs and Rb or Cs and Na and K.Contain Cs by combination, can bring into play reducing power effectively,, can realize the raising or the long lifetime of light emission luminance by the interpolation of injecting the territory to electronics.

In the present invention, also the electron injecting layer that is made of isolator or semi-conductor can be set further between negative electrode and organic layer.At this moment, can prevent the leakage of electric current effectively, improve the electronics injection.As such isolator, at least one metallic compound of selecting in the group of preferably using the halogenide of basic metal chalkogenide, alkaline-earth metal chalkogenide, alkali-metal halogenide and alkaline-earth metal to constitute.From can further improving the point of electronics injection, the preferred electron input horizon is made of these basic metal chalkogenides etc.Particularly, as the preferred as alkali chalkogenide, for example can enumerate Li ₂O, K ₂O, Na ₂S, Na ₂Se and Na ₂O as preferred bases great soil group metal chalcogenide, for example can enumerate CaO, BaO, SrO, BeO, BaS and CaSe.In addition, as the halogenide of preferred as alkali, for example can enumerate LiF, NaF, KF, LiCl, KCl and NaCl etc.In addition, as the halogenide of preferred alkaline-earth metal, for example can enumerate CaF ₂, BaF, SrF ₂, MgF ₂And BeF ₂And so on fluorochemical or fluorochemical beyond halogenide.

In addition, as the semi-conductor that constitutes electron supplying layer, can enumerate one or more the combination separately such as oxide compound, nitride or nitrogen oxide of at least a element that comprises Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn.In addition, the mineral compound of formation electron supplying layer is preferably microcrystal or amorphous insulativity film.If electron supplying layer is made of these insulativity films, then can form the more film of homogeneous, so can reduce blackspot pixel defectives such as (dark spot).In addition, as such mineral compound, can enumerate the halogenide of above-mentioned basic metal chalkogenide, alkaline-earth metal chalkogenide, alkali-metal halogenide and alkaline-earth metal etc.

(7) negative electrode

As negative electrode, inject electronics in order to inject transfer layer or luminescent layer to electronics, can use metal, alloy, electrical conductivity compound and their mixture of work function little (4eV is following) negative electrode as electrode substance.As the concrete example of such electrode substance, can enumerate sodium, Na-K alloy, magnesium, lithium, magnesium silver alloys, aluminium/aluminum oxide, Al-Li alloy, indium, olefines metal etc.

This negative electrode can form films with these electrode substances and makes by utilizing deposit or swashing method such as penetrate.

Take out from negative electrode under the luminous situation of spontaneous photosphere at this, the luminous relatively transmitance of negative electrode is preferably greater than 10%.

In addition, the sheet resistance as negative electrode is preferably below hundreds of Ω/.Thickness is generally 10nm～1 μ m, is preferably 50～200nm.

(8) insulation layer

Because organic EL applies electric field to ultrathin membrane, so the picture element flaw that leakage or short circuit cause takes place easily.In order to prevent this picture element flaw, preferably between pair of electrodes, insert the thin film layer of insulativity.

As the material that uses in the insulation layer, for example aluminum oxide, lithium fluoride, Lithium Oxide 98min, cesium fluoride, Cs2O, magnesium oxide, magnesium fluoride, calcium oxide, Calcium Fluoride (Fluorspan), aluminium nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, vanadium oxide etc. be can enumerate, their mixture or sandwich also can be used.

(9) method for manufacturing organic EL

Can form anode, luminescent layer, the injection transfer layer of hole as required and electronics as required and inject transfer layer, and then form negative electrode by utilizing above illustrative material and formation method, make organic EL.In addition can with from the negative electrode anode, with described opposite sequentially built organic EL.

Below be documented in the making example of the organic EL of the structure that sets gradually anode/hole injection layer/luminescent layer/electron injecting layer/negative electrode on the light-transmitting substrate.

At first, utilize methods such as deposit or sputter on suitable light-transmitting substrate, to form the film that constitutes by anode material, and make film become that 1 μ m is following, the thickness of preferred 10～200nm scope, make anode.Then, on this anode, hole injection layer is set.The formation of hole injection layer can utilize methods such as vacuum deposition method, spin-coating method, teeming practice, LB method to carry out as mentioned above, sets out but the point of pore etc. takes place for the film of the homogeneous that is easy to get calmly and being difficult to, and preferably utilizes vacuum deposition method to form.Utilizing vacuum deposition method to form under the situation of hole injection layer, this deposition conditions is according to the crystalline texture of the compound (material of hole injection layer) that uses, purpose hole injection layer or composite structure etc. and different, but usually in 50～450 ℃ of deposit source temperatures, vacuum tightness 10 ^-7～10 ^-3The scope of Torr, deposition speed 0.01～50nm/ second, substrate temperature-50～300 ℃, thickness 5nm～5 μ m is suitably selected.

Then, the formation that the luminescent layer of luminescent layer is set on hole injection layer also can be by using the luminous organic material that needs, utilize methods such as vacuum deposition method, sputter, spin-coating method, teeming practice that organic luminescent material thin-filmization is formed, but the point of pore etc. takes place for the film of the homogeneous that is easy to get calmly and being difficult to sets out, and preferably utilizes vacuum deposition method to form.Utilizing vacuum deposition method to form under the situation of luminescent layer, this deposition conditions is according to the compound that uses and difference, but can select in the condition and range identical with hole injection layer usually.

Then, on this luminescent layer, electron injecting layer is set.Identical with hole injection layer, luminescent layer, preferably utilize vacuum deposition method to form owing to must obtain the film of homogeneous.Deposition conditions can be selected from the condition and range identical with hole injection layer, luminescent layer.

Aromatic amine derivative of the present invention is different according to it is contained in which layer in light-emitting zone or cavity conveying zone, but under the situation of using vacuum deposition method, can with the other materials codeposition.In addition, use under the situation of spin-coating method, also can it be contained by mixing with other materials.

Thereby can obtain organic EL by stacked negative electrode at last.

Negative electrode is made of metal, can use sedimentation, sputter.But impaired for fear of to the organic matter layer system film of substrate the time, preferred vacuum deposition method.

The making of this organic EL is preferably constant always after taking out vacuum, is fabricated into negative electrode from anode.

Formation method to each layer of organic EL of the present invention is not particularly limited.Can use the formation method of the known in the past vacuum deposition method of utilization, spin-coating method etc.The organic thin film layer that contains the compound shown in the described general formula (1) that uses in organic EL of the present invention can form with vacuum deposition method, molecular ray sedimentation (MBE method) or the known method of utilizing the dip coating, spin-coating method, teeming practice, the rod that are dissolved in the solution in the solvent to be coated with coating processs such as method, rolling method.

Thickness to each organic layer of organic EL of the present invention is not particularly limited, if but because thickness is thin excessively usually, defectives such as pore take place easily then, if it is opposite blocked up, then must apply high-voltage, deterioration of efficiency is so be preferably the scope of several nm～1 μ m usually.

In addition, applying to organic EL under the situation of volts DS, anode is made as+, negative electrode is made as-polarity, if apply the voltage of 5～40V, then can observe luminous.In addition, even apply voltage with opposite polarity, electric current can not flow yet, fully can not be luminous.And then, applying under the situation of voltage of alternating current, only be made as at anode+, negative electrode is made as-polarity chron, can observe the luminous of homogeneous.The AC wave shape that applies can be random waveform.

Formation method to each layer of organic EL of the present invention is not particularly limited.Can use the formation method of the known in the past vacuum deposition method of utilization, spin-coating method etc.The organic thin film layer that contains the aromatic amines compound shown in the described general formula (1) that uses in organic EL of the present invention can form with vacuum deposition method, molecular ray sedimentation (MBE method) or the known method of utilizing the dip coating, spin-coating method, teeming practice, the rod that are dissolved in the solution in the solvent to be coated with coating processs such as method, rolling method.

Thickness to each organic layer of organic EL of the present invention is not particularly limited, if but if thickness is thin excessively usually, defectives such as pore then take place easily, if it is opposite blocked up, then must apply high-voltage, deterioration of efficiency is so be preferably the scope of several nm～1 μ m usually.

Aromatic amines compound of the present invention is owing to having aromatic series amino, so the solvability height of relative organic solvent.So, in utilizing wet type manufacturing process making organic EL, preferably used, even at the molecular weight height in compound of the present invention, be difficult to utilize under the film forming situation of vacuum deposition method, also can utilize dip coating, spin-coating method, teeming practice, rod to be coated with coating processs such as method, rolling method and easily form film.

Luminescent coating of the present invention forms and is made of the organic solvent solution that contains described aromatic amines compound with material.In addition, luminescent coating form be meant with material for example in organic EL, will participate in luminous organic compound layer, particularly the material that formation such as (conveyings) layer, electronics injection (conveying) layer are filmed and made is injected in luminescent layer, hole.

The organic solvent that uses in the dissolving as aromatic amines compound of the present invention can be enumerated non-halogen series solvent and halogen series solvent.

As non-halogen series solvent, can enumerate ether series solvents such as dibutyl ether, tetrahydrofuran (THF), dioxetane, methyl-phenoxide, pure series solvents such as methyl alcohol or ethanol, propyl alcohol, butanols, amylalcohol, hexanol, hexalin, methylcyclohexane, ethyl cellosolve, ethylene glycol, aromatic series such as benzene,toluene,xylene, ethylbenzene series solvent, hydrocarbon system solvents such as hexane, octane, decane, ester series solvents such as vinyl acetic monomer, N-BUTYL ACETATE, amyl acetate-n etc.Optimization aromatic series solvent in these non-halogen series solvents.

As the halogen series solvent, can enumerate methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, toluene(mono)chloride etc.

In addition, these solvents can use or mix multiple use separately.In addition, operable solvent is not limited to these.And then operable solvent is not limited to above-mentioned.

In addition, also can in forming with the solution of material, luminescent coating of the present invention dissolve doping agent as required in advance.As this doping agent, the amine compound that can use described general formula (I) or (II) represent.In addition, also can dissolve other various additives as required.

Embodiment

Then, the present invention is described in more detail to utilize embodiment, but the present invention is not limited by these examples fully.

Synthesis example 1 (synthesizing of compound 1)

The synthesis path of compound 1 is as follows.

[changing 34]

Intermediate 1-1 intermediate 1-2

Intermediate 1-3 intermediate 1-4

Intermediate 1-4

Intermediate 1-2 compound 1

(1-1) intermediate 1-1's is synthetic

Under argon atmospher, in toluene (90mL), add 1,3-diiodo-benzene (5.0g, 15mmol), the 4-chlorophenylboronic acid (5.7g, 36mmol), four (triphenylphosphinyl) palladium (0.87g, 0.75mmol), the aqueous sodium carbonate (45mL of 2mol/L, 90mmol), stirred 7 hours down at 80 ℃.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator (rotaryevaporator), (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (2.7g, yield 60%) to use silica gel column chromatography then.

(1-2) intermediate 1-2's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 1-1 (1.0g, 3.3mmol), 4-tertiary butyl aniline (1.2g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.3g, yield 76%) with silica gel column chromatography.

(1-3) intermediate 1-3's is synthetic

Under argon atmospher, and dissolving 4-chlorophenylboronic acid in toluene (80mL) (4.5g, 29mmol), 4-bromo-iodobenzene (7.3g, 26mmol), four (triphenylphosphinyl) palladium (0.6g, 0.52mmol), (40mL 80mmol) stirred 8 hours down at 80 ℃ the aqueous sodium carbonate of adding 2mol/L.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/4) resistates that obtains of purifying obtains white powder (3.1g, yield 44%) to use silica gel column chromatography then.

(1-4) intermediate 1-4's is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 1-3 (3.0g, 11mmol), N, two (4-xenyl) amine (3.2g of N-, 10mmol), three (dibenzalacetones), two palladiums (180mg, 0.2mmol), trimethyl carbinol sodium salt (1.4g, 15mmol), tri-butyl phosphine (65mg, 0.32mmol), stirred 8 hours down at 40 ℃.In reaction solution, add hexane, solid is separated out, use washed with methanol.Obtain shallow white solid (4.8g, yield 94%).

(1-5) compound 1 is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 1-2 (0.57g, 1mmol), intermediate 1-4 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.5g, yield 34%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₁₁₀H ₉₀N ₄=1466, measured value 1466 (M ⁺, 100)

Ionization potential: 5.22eV

Solvability (toluene): 5wt% is above solvable

Synthesis example 2 (synthesizing of compound 2)

The synthesis path of compound 2 is as follows.

[changing 35]

Intermediate 1-1 intermediate 2-1

Intermediate 1-3

Intermediate 2-2 intermediate 2-3

Intermediate 2-1 compound 2

(2-1) intermediate 2-1's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 1-1 (1.0g, 3.3mmol), aniline (0.78g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.1g, yield 81%) with silica gel column chromatography.

(2-2) intermediate 2-2's is synthetic

Under argon atmospher, in dry toluene (10mL), add 9,9-dimethyl-2-bromine fluorenes (1.8g, 6.6mmol), aniline (1.56g, 16mmol), three (dibenzalacetones), two palladiums (0.12g, 0.13mmol), trimethyl carbinol sodium salt (1.9g, 20mmol), tri-butyl phosphine (40mg, 0.2mmol), stirred 8 hours down at 80 ℃.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.5g, yield 81%) with silica gel column chromatography.

(2-3) intermediate 2-3's is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 1-3 (3.0g, 11mmol), intermediate 2-2 (0.93g, 10mmol), three (dibenzalacetone) two palladium (180mg, 0.2mmol), trimethyl carbinol sodium salt (1.4g, 15mmol), (65mg 0.32mmol), at room temperature stirred 8 hours tri-butyl phosphine.In reaction solution, add hexane, solid is separated out, use washed with methanol, obtain intermediate 2-3 (3.5g, yield 75%).

(2-4) compound 2 is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 2-1 (0.41g, 1mmol), intermediate 2-3 (1.1g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.6g, yield 47%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₉₈H ₇₄N ₄=1282, measured value 1282 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 3 (synthesizing of compound 3)

The synthesis path of compound 3 is as follows.

[changing 36]

Intermediate 1-2 compound 3

Under argon atmospher, in dry toluene (20mL), add intermediate 1-2 (0.53g, 1mmol), intermediate 2-3 (1.1g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.25g, yield 18%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₁₀₄H ₉₀N ₄=1394, measured value 1394 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 4 (synthesizing of compound 4)

The synthesis path of compound 4 is as follows.

[changing 37]

Intermediate 4-1

Intermediate 4-1 compound 4

(4-1) intermediate 4-1's is synthetic

Under argon atmospher, in dry toluene (10mL), add 9,9-dioctyl-2-bromine fluorenes (1.1g, 3.3mmol), aniline (0.78g, 8.3mmol), three (dibenzalacetones), two palladiums (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), tri-butyl phosphine (20mg, 0.1mmol), stirred 8 hours down at 80 ℃.(eluting solvent: purification reaction liquid methylene dichloride) obtains white solid (0.97g, yield 85%) with silica gel column chromatography.

(4-2) compound 4 is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 4-1 (0.58g, 1mmol), intermediate 2-3 (1.1g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.5g, yield 35%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₁₀₇H ₁₀₂N ₄=1442, measured value 1442 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 5 (synthesizing of compound 5)

The synthesis path of compound 5 is as follows.

[changing 38]

Intermediate 5-1 intermediate 5-2

Intermediate 5-3 intermediate 5-4

Compound 5

(5-1) intermediate 5-1's is synthetic

Under argon atmospher, in toluene (90mL), add 3-bromo-1-iodobenzene (10g, 36mmol), 4-chlorophenylboronic acid (5.7g, 36mmol), four (triphenylphosphinyl) palladium (0.87g, 0.75mmol), (45mL 90mmol), stirred 7 hours down at 80 ℃ for the aqueous sodium carbonate of 2mol/L.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (7.2g, yield 75%) to use silica gel column chromatography then.

(5-2) intermediate 5-2's is synthetic

Under argon atmospher, (3g 11mmol), is cooled to after-20 ℃ dissolving intermediate 5-1, and (8.1g 13mmol), stirred 1 hour slowly to add n-Butyl Lithium 1.6M hexane solution in the mixed solution of anhydrous tetrahydro furan (20mL) and dry toluene (20mL).Be cooled to-60 ℃, (4.1g, anhydrous tetrahydrofuran solution 22mmol) (10mL) stirred 2 hours, were warming up to room temperature then, stirred 5 hours to add tri-isopropylborate in reaction solution.Add 1N hydrochloric acid (30mL), stirred 30 minutes, separate organic layer.Use the vaporizer concentrating under reduced pressure,, obtain intermediate 5-2 (1.6g, yield 64%) with the resistates that silica gel column chromatography (hexane/ethyl acetate=1/1) purifying obtains.

(5-3) intermediate 5-3's is synthetic

Under argon atmospher, in toluene (40mL), add intermediate 5-1 (1.7g, 6.5mmol), intermediate 5-2 (1.5g, 6.5mmol), four (triphenylphosphinyl) palladium (0.22g, 0.2mmol), (10mL 20mmol), stirred 7 hours down at 80 ℃ for the aqueous sodium carbonate of 2mol/L.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains intermediate 5-3 (1.8g, yield 74%) to use silica gel column chromatography then.

(5-4) intermediate 5-4's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 5-3 (1.2g, 3.3mmol), aniline (0.78g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains intermediate 5-4 (1.3g, yield 80%) with silica gel column chromatography.

(5-5) compound 5 is synthetic

Under argon atmospher; in dry toluene (20mL), add intermediate 5-4 (0.49g; 1mmol), N-(4 '-bromo biphenyl base-4-acyl group)-N-(1-naphthyl)-N-aniline (1.1g; 2.4mmol), three (dibenzalacetone) two palladium (73mg; 80 μ mol), trimethyl carbinol sodium salt (0.29g; 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.58g, yield 47%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₉₂H ₆₆N ₄=1226, measured value 1226 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 6 (synthesizing of compound 6)

The synthesis path of compound 6 is as follows.

[changing 39]

Intermediate 5-3 intermediate 6-1

Compound 6

(6-1) intermediate 6-1's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 5-3 (1.2g, 3.3mmol), 4-tertiary butyl aniline (1.2g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.5g, yield 76%) with silica gel column chromatography.

(6-2) compound 6 is synthetic

Under argon atmospher, in toluene (20mL), add intermediate 6-1 (0.6g, 1mmol), intermediate 1-4 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.45g, yield 29%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

Synthesis example 7 (synthesizing of compound 7)

The synthesis path of compound 7 is as follows,

[changing 40]

Intermediate 7-1 intermediate 7-2

Intermediate 7-3 intermediate 7-4

Intermediate 7-5 intermediate 7-6

Compound 7

(7-1) intermediate 7-1's is synthetic

Under argon atmospher, in toluene (90mL), add 4-bromo-1-iodobenzene (10g, 36mmol), 4-chlorophenylboronic acid (5.7g, 36mmol), four (triphenylphosphinyl) palladium (0.87g, 0.75mmol), (45mL 90mmol), stirred 7 hours down at 80 ℃ for the aqueous sodium carbonate of 2mol/L.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (7.7g, yield 81%) to use silica gel column chromatography then.

(7-2) intermediate 7-2's is synthetic

Under argon atmospher, (3g 11mmol), is cooled to after-20 ℃ dissolving intermediate 7-1, and (8.1g 13mmol), stirred 1 hour slowly to add n-Butyl Lithium 1.6M hexane solution in the mixed solution of anhydrous tetrahydro furan (20mL) and dry toluene (20mL).Be cooled to-60 ℃, (4.1g, anhydrous tetrahydrofuran solution 22mmol) (10mL) stirred 2 hours, were warming up to room temperature then, stirred 5 hours to add tri-isopropylborate in reaction solution.Add 1N hydrochloric acid (30mL), stirred 30 minutes, separate organic layer.Use the vaporizer concentrating under reduced pressure,, obtain intermediate 7-2 (1.8g, yield 70%) with the resistates that silica gel column chromatography (hexane/ethyl acetate=1/1) purifying obtains.

(7-3) intermediate 7-3's is synthetic

Under argon atmospher, in toluene (20mL), add 3-bromo-1-iodobenzene (1.4g, 5mmol), intermediate 7-2 (1.2g, 5mmol), four (triphenylphosphinyl (ホス Off イノ)) palladium (0.17g, 0.15mmol), the aqueous sodium carbonate (7.55mL of 2mol/L, 15mmol), stirred 7 hours down at 80 ℃.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (1.2g, yield 70%) to use silica gel column chromatography then.

(7-4) intermediate 7-4's is synthetic

Under argon atmospher, and dissolving intermediate 7-3 in the mixed solution of anhydrous tetrahydro furan (10mL) and dry toluene (10mL) (1.2g, 3.5mmol), be cooled to after-20 ℃, (2.6mL 4.2mmol), stirred 1 hour slowly to add n-Butyl Lithium 1.6M hexane solution.Be cooled to-60 ℃, (1.3g, anhydrous tetrahydrofuran solution 7mmol) (10mL) stirred 2 hours, were warming up to room temperature then, stirred 5 hours to add tri-isopropylborate in reaction solution.Add 1N hydrochloric acid (30mL), stirred 30 minutes, separate organic layer.Use the vaporizer concentrating under reduced pressure,, obtain intermediate 7-4 (0.6g, yield 56%) with the resistates that silica gel column chromatography (hexane/ethyl acetate=1/1) purifying obtains.

(7-5) intermediate 7-5's is synthetic

Under argon atmospher, in toluene (10mL), add intermediate 7-3 (0.66g, 1.9mmol), intermediate 7-4 (0.6g, 1.9mmol), four (triphenylphosphinyl) palladium (0.07g, 0.06mmol), (2.9mL 5.7mmol), stirred 7 hours down at 80 ℃ for the aqueous sodium carbonate of 2mol/L.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (0.68g, yield 68%) to use silica gel column chromatography then.

(7-6) intermediate 7-6's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 7-5 (1.7g, 3.3mmol), 4-tertiary butyl aniline (1.2g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.5g, yield 60%) with silica gel column chromatography.

(7-7) compound 7 is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 7-6 (0.75g, 1mmol), intermediate 1-4 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.54g, yield 32%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₁₂₈H ₁₀₂N ₄=1694, measured value 1694 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 8 (synthesizing of compound 8)

The synthesis path of compound 8 is as follows.

[changing 41]

Intermediate 7-2 intermediate 8-1

Intermediate 8-2

Compound 8

(8-1) intermediate 8-1's is synthetic

Under argon atmospher, in toluene (80mL), add intermediate 7-2 (1.7g, 13mmol), 1, the 3-dibromobenzene (1.5g, 6.5mmol), four (triphenylphosphinyl) palladium (0.44g, 0.4mmol), the aqueous sodium carbonate (20mL of 2mol/L, 40mmol), stirred 7 hours down at 80 ℃.Separate organic layer, clean, use anhydrous magnesium sulfate drying then with saturated brine.Concentrate organic layer with rotatory evaporator, (eluting solvent: the dichloromethane/hexane=1/3) resistates that obtains of purifying obtains white powder (2.6g, yield 90%) to use silica gel column chromatography then.

(8-2) intermediate 8-2's is synthetic

Under argon atmospher, in dry toluene (10mL), add intermediate 8-1 (1.5g, 3.3mmol), 4-tertiary butyl aniline (1.2g, 8.3mmol), three (dibenzalacetone) two palladium (60mg, 66 μ mol), trimethyl carbinol sodium salt (0.95g, 9.9mmol), (20mg 0.1mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: purification reaction liquid methylene dichloride) obtains shallow white solid (1.8g, yield 79%) with silica gel column chromatography.

(8-3) compound 8 is synthetic

Under argon atmospher, in dry toluene (20mL), add intermediate 8-2 (0.67g, 1mmol), intermediate 1-4 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.50g, yield 38%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₉₈H ₈₂N ₄=1314, measured value 1314 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Synthesis example 9 (synthesizing of compound 9)

The synthesis path of compound 9 is as follows.

[changing 42]

Intermediate 5-4 compound 9

Under argon atmospher, in dry toluene (20mL), add intermediate 5-4 (0.67g, 1mmol), intermediate 2-3 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.33g, yield 24%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₉₈H ₈₂N ₄=1358, measured value 1358 (M ⁺, 100)

Solvability (toluene): 1wt% is above solvable

Embodiment 1 (making of organic EL)

The glass substrate of the band ito transparent electrode that ultrasonic cleaning 25mm * 75mm * 1.1mm is thick in Virahol (ジオマテイ Star Network corporate system) 5 minutes carries out 30 minutes UV ozone clean then.On this substrate, use spin-coating method, the polyethylene dioxythiophene polystyrolsulfon acid (being designated hereinafter simply as PEDOTPSS) that uses in the thickness film forming hole injection layer with 40nm.Then, use the solution (1 quality %) that compound 1 is dissolved in gained in the toluene, with the thickness of spin-coating method, film forming hole transporting layer on PEDOTPSS.The thickness of this moment is 50nm.On this film, utilize the following compd A of vacuum deposition film forming.The thickness of this moment is 40nm.Simultaneously, as light emitting molecule, the following styrylamine compd B of deposit makes the weight ratio of A and B become 40: 2.This film plays the effect of luminescent layer.Then, three of film forming thickness 10nm (oxine) aluminium film (is designated hereinafter simply as " Alq film ".)。This Alq film plays the effect of electron supplying layer.サエスゲ Star one corporate system) and Alq the binary deposit is as the Li of reductibility doping agent (Li source:, form the Alq:Li film as electron injecting layer (negative electrode) then.Depositing metal Al on this Alq:Li film forms metallic cathode, forms organic EL luminous element.This element sends blue light.At 10mA/cm ²Luminous efficiency and luminosity 1000cd/m ²The brightness of the element when making it luminous down life-span of partly declining is as shown in table 1.

[changing 43]

Compound 1

Compd A compd B Alq

Embodiment 2

In embodiment 1, use following compound 2 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 44]

Embodiment 3

In embodiment 1, use following compound 3 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 45]

Compound 3

Embodiment 4

In embodiment 1, use following compound 4 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 46]

Compound 4

Embodiment 5

In embodiment 1, use following compound 5 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 47]

Compound 5

Embodiment 6

In embodiment 1, use following compound 6 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 48]

Compound 6

Embodiment 7

In embodiment 1, use following compound 7 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 49]

Compound 7

Embodiment 8

In embodiment 1, use following compound 8 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 50]

Compound 8

Embodiment 9

In embodiment 1, use following compound 9 to replace compound 1, in addition, similarly carry out, make organic EL.The result is as shown in table 1.

[changing 51]

Compound 9

Comparative example 1

In embodiment 1, use following Compound C to replace compound 1, attempt the toluene solution of preparation 1 quality %.But Compound C is not dissolved in toluene, becomes gonorrhoea.

[changing 52]

Compound C

Comparative example 2

In embodiment 1, use following Compound D to replace compound 1, attempt the toluene solution of preparation 1 quality %.But Compound D is not dissolved in toluene, becomes gonorrhoea.

[changing 53]

Compound D

[table 1]

Table 1

Embodiment	1	2	3	4	5	6	7	8	9
Embodiment	1	2	3	4	5	6	7	8	9	Luminous efficiency (cd/A)	8.6	7.9	8.1	8.6	7.8	8.2	8.3	8.1	8.0
Brightness partly declines the life-span (time)	1000	1250	1100	1050	1200	1050	900	950	1000	Luminous efficiency (cd/A)	8.6	7.9	8.1	8.6	7.8	8.2	8.3	8.1	8.0

Embodiment 10 (making of organic EL)

The glass substrate of the band ito transparent electrode that ultrasonic cleaning 25mm * 75mm * 1.1mm is thick in Virahol (ジオマテイ Star Network corporate system) 5 minutes carries out 30 minutes UV ozone clean then.On this substrate, use spin-coating method, the polyethylene dioxythiophene polystyrolsulfon acid (being designated hereinafter simply as PEDOTPSS) that uses in the thickness film forming hole injection layer with 100nm.Then, with spin-coating method, the thickness of 20nm, the toluene solution of film forming compound 1 (0.6 quality %), 170 ℃ are following dry 30 minutes.

Then, use following compd E: compound F 17-hydroxy-corticosterone (E: F=20: 1 quality % toluene/isopropanol solution (toluene/isopropanol=1/2 (mass ratio)) 2 (mass ratioes)), with spin-coating method film forming luminescent layer.The thickness of this moment is 40nm.The Alq film of film forming thickness 10nm on this film.This Alq film plays the effect of electron supplying layer.サエスゲ Star one corporate system) and Alq the binary deposit is as the Li of reductibility doping agent (Li source:, form the Alq:Li film as electron injecting layer (negative electrode) then.Depositing metal Al on this Alq:Li film forms metallic cathode, forms organic EL luminous element.This element sends blue light, at luminosity 100cd/m ²Under voltage and luminous efficiency as shown in table 2.

[changing 54]

[changing 55]

The compd E compound F 17-hydroxy-corticosterone

Synthesis example 10 (synthesizing of compound 10)

Compound 10 synthetic as follows.

[changing 56]

Intermediate 4-1

Compound 10

Under argon atmospher, in dry toluene (20mL), add intermediate 4-1 (0.57g, 1mmol), intermediate 1-4 (1.2g, 2.4mmol), three (dibenzalacetone) two palladium (73mg, 80 μ mol), trimethyl carbinol sodium salt (0.29g, 3mmol), (26mg 0.13mmol), stirred 8 hours down at 80 ℃ tri-butyl phosphine.(eluting solvent: (eluting solvent: dichloromethane/hexane=1/3) purification reaction liquid obtains yellow solid (0.35g, yield 23%) methylene dichloride), then to use silica gel column chromatography with silica gel column chromatography.

FD-MS: calculated value C ₁₁₃H ₁₀₂N ₄=1514, measured value 1514 (M ⁺, 100)

Ionization potential: 5.14eV

Solvability (toluene): 5wt% is above solvable

Embodiment 11

Use following compound 10 to replace compound 1, in addition, make element similarly to Example 10.The result is as shown in table 2.

[changing 57]

Compound 10

Embodiment 12

Use following compound 6 to replace compound 1, in addition, make element similarly to Example 10.The result is as shown in table 2.

[changing 58]

Compound 6

Embodiment 13

Use following compound 3 to replace compound 1, in addition, make element similarly to Example 10.The result is as shown in table 2.

[changing 59]

Compound 3

Comparative example 3

Use following compound G to replace compound 1, in addition, make element similarly to Example 10.The result is as shown in table 2.

[changing 60]

Compound G

[table 2]

Table 2

	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 3
	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 3	Voltage (V)	5.5	5.5	5.5	5.5	5.5
Luminous efficiency (cd/A)	3.5	2.9	2.8	2.9	1.5	Voltage (V)	5.5	5.5	5.5	5.5	5.5

The compound that shows in present technique even coating forms luminescent layer, also can demonstrate high luminous efficiency owing to have the suitable solvability and the solvent resistance of film.On the other hand,, use under the situation of compound G, compare, demonstrate low luminous efficiency with present technique as represented at comparative example 3.This may be because when coating formed luminescent layer, solvent have been cut down the film of hole transporting layer, the thickness attenuation, and carrier balance is greatly destroyed.

Utilizability on the industry

Such as above detailed description, the dissolubility of aromatic amines compound of the present invention is high, in the manufacturing of the organic EL that uses this compound, the coating that can utilize film to form solution carry out stackedization, can carry out the wet type film forming, use the organic EL of this compound to present various luminous tones, heat resistance is high, if particularly use aromatic amines compound of the present invention to inject, carry material as the hole, then hole injection, transporting height, luminosity and luminous efficiency are high, and the life-span is long. So the practicality of organic EL of the present invention is high, can be as the flat luminous body of wall hanging TV set or the light sources such as backlight of display.

Claims

1. aromatic amines compound, it is with following general formula (1) expression,

[changing 1]

[in the general formula 1, Ar ₁～Ar ₆Expression replaces or does not have the aryl of carbonatoms 6～40 in the ring of replacement or replace or do not have the heteroaryl of carbonatoms 3～40 in the ring of replacement independently respectively, also has Ar ₁And Ar ₂, and Ar ₅And Ar ₆Also can link by singly-bound respectively and form carbazyl,

R ₁～R ₄Represent halogen atom, carboxyl, amino, hydroxyl respectively independently, replace or do not have the carbonatoms 1～40 of replacement alkyl, replace or do not have the carbonatoms 2～40 of replacement alkenyl, replace or do not have replacement carbonatoms 2～40 alkynyl or replace or do not have the alkoxyl group of the carbonatoms 1～40 of replacement

N, m, p and q are respectively 0～4 integer,

-(Ar ₇) _n-(Ar ₈) _b-(Ar ₉) _c- (2)

In the general formula (2), Ar ₇～Ar ₉Be respectively above-mentioned Ar ₁～Ar ₆The group of expression forms the group of divalent,

A, b and c are respectively 1～3 integer,

[changing 2]

In the general formula (3), R ₆And R ₇Respectively with above-mentioned R ₁～R ₄Identical, and R ₆And R ₇Also can link mutually and form ring structure].

2. aromatic amines compound according to claim 1, wherein,

Described aromatic amines compound is the organic electroluminescent device material.

3. aromatic amines compound according to claim 1, wherein,

Described aromatic amines compound is an organic electroluminescent device with hole transporting material or organic electroluminescent device hole-injecting material.

4. organic electroluminescent device, it uses one or more layers organic thin film layer that constitutes of pair of electrodes clamping that is made of anode and negative electrode to form, wherein,

One deck at least of this organic thin film layer contains the described aromatic amines compound of claim 1.

5. organic electroluminescent device according to claim 4, wherein,

Described organic thin film layer has cavity conveying zone and/or hole injection zone, and described aromatic amines compound is contained in this cavity conveying zone and/or hole injection zone.

6. organic electroluminescent device according to claim 5, wherein,

Described cavity conveying zone and/or hole injection zone contain described aromatic amines compound as main component.

7. according to each described organic electroluminescent device in the claim 4～6, wherein,

Described cavity conveying zone and/or hole injection zone mainly contain described aromatic amines compound, and luminescent layer utilizes vacuum deposition and makes.

8. according to each described organic electroluminescent device in the claim 4～6, wherein,

Described cavity conveying zone and/or hole injection zone mainly contain described aromatic amines compound, and luminescent layer utilizes the wet type film forming and makes.

9. an organic electroluminescent is used with film and is formed solution, wherein,

Contain more than the described aromatic amines compound 0.1 quality % of claim 1.