JPH05163488A - Electroluminescent element of organic thin film - Google Patents

Abstract

PURPOSE:To obtain an electroluminescence element having strong emission intensity, high durability and practical level. CONSTITUTION:In an electroluminescent element composed of a pair of counter electrodes and one or plural layers of an organic compound layer sandwiched in between the electrodes, at least one layer containing a specific polycyclic quinone compound and at least one layer containing a styryl compound are laid in the element to give an electroluminescent element of organic thin film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film electroluminescent device, and more particularly to a thin film electroluminescent device used for flat light sources, flat displays and the like.

[0002]

2. Description of the Related Art An electroluminescence device is composed of an organic light emitting layer and a pair of counter electrodes sandwiching the organic light emitting layer, the light emission of which is injected from one electrode and from the other electrode. The holes cause recombination in the light-emitting layer to excite the light-emitting body to a higher energy level, and emit the energy as light when the excited light-emitting body returns to its original ground state.
In such a carrier injection type electroluminescence device, a thin film organic compound has been used as a light emitting layer, and a device having a strong light emission intensity has been obtained. For example, U.S. Pat. No. 3,530,325 uses a single crystal anthracene or the like as a light emitter, and JP-A-59-194393 discloses a combination of a hole injection layer and an organic light-emitting layer.
63-295695 includes a combination of a hole injecting and transporting layer and an organic electron injecting and transporting layer, and Jpn. Journal of Applied Physics, v.
ol27, No2, P269-271 discloses a combination of a hole transfer layer, a light emitting layer, and an electron transfer layer, and the emission intensity has been improved so far.

However, in the conventional electroluminescent device having the above-mentioned structure, although the emission intensity has been improved, there is a problem in durability, and the emission intensity and durability at the practical level have not yet been reached. Therefore,
It has been desired to develop an electroluminescence device having higher emission intensity and higher durability.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an electroluminescence device having a higher emission intensity and higher durability at a practical level.

[0005]

As a result of intensive research to achieve the above object, the inventors of the present invention have found that an electro device including a pair of counter electrodes and a plurality of organic compound layers sandwiched therebetween. In the luminescence device, a layer containing an organic compound represented by the following general formula [I], and a layer containing a styryl compound represented by the following general formula [II], at least one or more layers respectively It was found that this can be achieved by the organic thin film electroluminescence device.

[0006]

[Chemical 3]

(Z1) of the residue Z of the general formula [I]
In (Z4), R _{1 to} R ₁₁ are each independently a hydrogen atom,
Halogen atom, substituted or unsubstituted 5 groups; alkyl group, monovalent group derived from unsaturated chain hydrocarbon, heterocyclic group, aryl group, group containing 2 or more nitrogen atoms, or styryl group , Anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl group, acyl group, aryloxyl group, aralkyl group, acylamino group, acyloxyl group Represents a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a sulfonium group, and represents R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₆
And R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , and R ₁₀ and R ₁₁ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure. Good.

Further, (Z5) of the residue Z of the above general formula [I]
Inside X represents a substituted or unsubstituted heterocycle.

Further, in the general formula [II] above, R ₁₂ and R
₁₃ is each independently a hydrogen atom, a substituted or unsubstituted four groups described below; an alkyl group, a heterocyclic group, an aryl group,
Represents a monovalent group derived from an unsaturated chain hydrocarbon, R
₁₂ and R ₁₃ may combine with each other to form a substituted or unsubstituted saturated or unsaturated ring structure.

R ₁₄ is the following three groups which are substituted or unsubstituted; an alkyl group, an aryl group, an alkoxy group, or
_{{P (C 6 H 4)} } - CH = C {(- R 12) (- R 13)} represents, R ₁₂ and R ₁₃ are as defined above.

R ₁₅ represents a hydrogen atom, the following three substituted or unsubstituted groups; an alkyl group, an aryl group and an alkoxy group.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Residues (Z-1) of the general formula [I]
(Z-5) and the halogen atom represented by the general formula [II] are chlorine atom, bromine atom, fluorine atom and iodine atom; the substituted or unsubstituted alkyl group is methyl group, ethyl group, propyl group and butyl group. , Alkyl groups such as cyclohexyl groups; monovalent groups derived from substituted or unsubstituted unsaturated chain hydrocarbons are vinyl, 1-propenyl, propyl, allyl, isopropenyl, 1-butenyl Group, monovalent group derived from unsaturated chain hydrocarbon such as 2-butenyl group, 2-pentenyl group, ethynyl group; piperidyl group, piperidino group, pyrrolyl group as substituted or unsubstituted heterocyclic group , Furyl group, cenyl group, imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group, thiazolyl group, pyridazinyl group, monovalent group consisting of pyridone, morpholyl Heterocyclic groups such as nyl group, morphonilino group, oxazolyl group, isoxazolyl group, isothiazolyl group, pyrimidinyl group, pyrazinyl group, pyranyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, quinolyl group; substituted or unsubstituted Aryl groups such as phenyl group, naphthyl group, anthonyl group, xylyl group, biphenyl group, phenanthryl group and the like; groups containing two or more substituted or unsubstituted nitrogen atoms are azo group, phenylazo group, naphthyrazo group, hydranizo group Groups containing two or more nitrogen atoms such as groups, hydrazo groups, azoxy groups, azido groups, diazoamino groups, amidino groups, ureylene groups, guanidino groups; as alkoxyl groups methoxyl groups, ethoxyl groups, propoxyl groups, butoxyl groups, pentyl Oxyl , Alkoxyl groups such as hexyloxyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and other alkoxycarbonyl groups; aminocarbonyl groups such as anilinocarbonyl group, dimethylaminocarbonyl group, larvamoyl group, alanyl Groups such as aminocarbonyl groups; aryloxycarbonyl groups such as naphthyloxycarbonyl groups, xylyloxycarbonyl groups and phenoxycarbonyl groups such as aryloxycarbonyl groups; acyl groups such as formyl, acetyl, propionyl, butyryl, Pareryl group, oaluminoyl group, stearoyl group, oleoyl group, benzoyl group, trioyl group, salicyloyl group, cinnamoyl group, naphthoyl group, phthaloyl group, oxali Groups, malonyl groups, succinyl groups, furoyl groups and other acyl groups; aryloxyl groups such as phenoxy and tolyloxy groups and other aryloxyl groups; aralkyl groups such as benzyl and phenethyl groups; aralkyl groups such as acetyl Acylamino group such as amino group, propionylamino group, butyrylamino group; acetyloxy group as acyloxyl group,
An acyloxyl group such as a propionyloxy group and a butyryloxy group.

The above-mentioned substituents include hydrogen atom, halogen atom, alkyl group such as methyl group, ethyl group, propyl group, butyl group and cyclohexyl group, vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-
Monovalent groups derived from unsaturated chain hydrocarbons such as butenyl group, 2-pentenyl group, ethynyl group, piperidyl group,
Piperidino group, pyrrolyl group, furyl group, cenyl group,
Monovalent group consisting of imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group, thiazolyl group, pyridazinyl group, pyridone, morpholinyl group, morpholinino group, oxazolyl group, isoxazolyl group, isothiazolyl group,
Heterocyclic groups such as pyrimidinyl group, pyrazinyl group, pyranyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, quinolyl group, aryl such as phenyl group, naphthyl group, anthonyl group, xylyl group, biphenyl group, phenanthryl group Group, azo group, phenylazo group, naphthyrazo group, hydranizo group, hydrazo group, azoxy group, azido group, diazoamino group, group containing two or more nitrogen atoms such as amidino group, ureylene group, guanidino group, styryl group, anisyl group, Alkoxy groups such as amino group, alkylamino group, dialkylamino group, methoxyl group, ethoxyl group, propoxyl group, butoxyl group, pentyloxyl group, hexyloxyl group, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, etc. Aminocarbonyl groups such as oxycarbonyl group, anilinocarbonyl group, dimethylaminocarbonyl group, larvamoyl group, alanyl group, naphthyloxycarbonyl group, xylyloxycarbonyl group, aryloxycarbonyl group such as phenoxycarbonyl group, carboxyl group, formyl Group, acetyl group, propionyl group, butyryl group, pareryl group, oaluminoyl group, stearoyl group, oleoyl group, benzoyl group, trioyl group, salicyloyl group, cinnamoyl group, naphthoyl group, phthaloyl group, oxalyl group, malonyl group, succinyl group , Acyl group such as furoyl group, aryloxy group such as phenoxy group and tolyloxy group, aralkyl group such as benzyl group and phenethyl group, acetylamino group, propionylamino group, butyrylamino An acylamino group, an acetyloxy group, such as, propionyloxy group, acyloxy group such as butyryloxy group, a hydroxyl group, a cyano group, a nitro group, a sulfo group or a sulfonium group.

Specific examples of such an organic compound represented by the general formula [I] include those shown below.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

[0031]

[Chemical 20]

[0032]

[Chemical 21]

[0033]

[Chemical formula 22]

[0034]

[Chemical formula 23]

[0035]

[Chemical formula 24]

[0036]

[Chemical 25]

Next, specific examples of the styryl compound represented by the general formula [II] are shown.

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

[0040]

[Chemical 28]

[0041]

[Chemical 29]

[0042]

[Chemical 30]

[0043]

[Chemical 31]

[0044]

[Chemical 32]

[0045]

[Chemical 33]

[0046]

[Chemical 34]

[0047]

[Chemical 35]

[0048]

[Chemical 36]

[0049]

[Chemical 37]

[0050]

[Chemical 38]

[0051]

[Chemical Formula 39]

These are only specific examples shown for the purpose of explanation and do not limit the scope of the claims of the present invention.

The organic compound represented by the general formula [I] of the present invention can be easily synthesized by a known method (described in J. Chem. Soc, 1957, 4616, etc.).

Synthesis Example 1 Chloranil (21 g; mp287 ° C.), maleic anhydride (150 g; mp55.5 ° C.) and perylene (10 g; mp280) were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel.
℃) Put the mixture that has been sufficiently crushed and mixed, and while heating, add 10
Stir for minutes. Then, warmed xylene (200 ml) was added from the dropping funnel, stirred and boiled for 1 hour, and hot filtered. The reddish brown needle-like crystals separated by hot filtration were washed with xylene and further thoroughly washed with ether to obtain reddish-brown needle-like crystals. The obtained reddish brown needle crystals were sublimated for 4 hours and a half at 300 ° C and 10 ^-4 mmHg using a vacuum sublimation device, and the sublimation residue was further used at 400 ° C and 10 ^-4 mmHg for 6 hours using a vacuum sublimation device. By processing, glossy reddish brown needle crystals (I-2
8) was obtained.

Synthetic Example 2 (I-28) synthesized in Synthetic Example 1 with o-phenylenediamine as a non-reactive solvent, preferably N-methylpyrrolidone,
Aprotic solvent such as N, N-dimethylformamide; basic solvent such as quinoline; chlorine-based solvent such as o-dichlorobenzene, alone or in a mixed solvent, at room temperature or higher, preferably 150 to 250
By conducting a condensation reaction under a temperature condition of ℃ (I-1)
Can be synthesized.

Synthesis Example 3 2,3-diaminonaphthalene was added to (I-28) synthesized in Synthesis Example 1 as a non-reactive solvent, preferably an aprotic solvent such as N-methylpyrrolidone or N, N-dimethylformamide; A basic solvent such as quinoline; a chlorine-based solvent such as o-dichlorobenzene, alone or in a mixed solvent, is subjected to condensation reaction at room temperature or higher, preferably at 150 to 250 ° C to synthesize (I-2). be able to.

Synthetic Example 4 (I-28) synthesized in Synthetic Example 1 with aniline as a non-reactive solvent, preferably an aprotic solvent such as N-methylpyrrolidone or N, N-dimethylformamide; basic such as quinoline. Solvent; (I-37) can be synthesized by subjecting a condensation reaction to a chlorine-based solvent such as o-dichlorobenzene alone or in a mixed solvent under a temperature condition of room temperature or higher, preferably 150 to 250 ° C.

Synthesis Example 5 1,8-Diaminonaphthalene was added to (I-28) synthesized in Synthesis Example 1 as a non-reactive solvent, preferably an aprotic solvent such as N-methylpyrrolidone or N, N-dimethylformamide;
A basic solvent such as quinoline; a chlorine-based solvent such as o-dichlorobenzene, alone or in a mixed solvent, at room temperature or higher, preferably 150
By conducting the condensation reaction under the temperature condition of ~ 250 ° C (I-
95) can be synthesized.

The styryl compound represented by the general formula [II] of the present invention can be easily produced by a known method.

The styryl compound represented by the general formula [II] can be obtained, for example, by reacting a phosphorus compound represented by the following general formula [III] with a diformyl compound represented by the general formula [IV].

[0061]

[Chemical 40]

In the general formula [III], R ₁₂ and R ₁₃ have the same meanings as [II], and X is a triphenylphosphonium group represented by -P ⁺ -(R ₁₆ ) ₃ Y-, or a trialkylphosphonium salt. Or a dialkyl phosphite group represented by —PO (OR ₁₇ ) ₂ . R ₁₆ represents an alkyl group or an aryl group, and Y
Represents a halogen ion, and R ₁₇ represents an alkyl group.

In the general formula [IV], R ₁₄ and R ₁₅ have the same meanings as [II].

The phosphorus compound represented by the general formula [III] can be easily prepared by heating the corresponding halomethyl compound and triarylphosphine or trialkylsulfin, or trialkyl phosphite directly or in a solvent such as toluene or xylene. Can be manufactured.

As a reaction solvent in the method for synthesizing the styryl compound, an inert solvent such as hydrocarbons, alcohols and ethers is preferable, and methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxy are preferable. Ethane, bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-
Examples include imidazolidinone. Among them, polar solvents,
For example, N, N-dimethylformamide and dimethyl sulfoxide are suitable.

As the condensing agent, caustic soda, caustic potash, sodium amide hydride and sodium methylate, and alcoholates such as potassium t-butoxide are used. The reaction temperature is about 0 depending on the stability of the solvent used for the condensing agent, the reactivity of the condensing component, and the reactivity of the condensing agent.
A wide range can be selected from 0 ° C to about 100 ° C, preferably 10 to 80 ° C.

Synthesis Example 6 Diethyl benzylphosphonate (2.28 g) and triphenylamine-4,4-dicarbaldehyde (1.50 g) were added to 1,2-dimethoxyethane (20 ml), and 50% sodium hydride (0.50 g) was added thereto at room temperature. The mixture was stirred for 3 hours and reacted. After that, the mixture was heated to reflux for about 30 minutes. After cooling to room temperature, the reaction mixture is washed with water 20
Pour into 0 ml, filter the precipitate formed, wash with water and dry.
1.46 g (65% yield) of powder was obtained. Further, this powder was recrystallized from ethyl acetate and methanol to obtain a pale yellowish exemplary compound (II-16).

The melting point of the obtained styryl compound is 134 to 137.
It was ℃.

The organic thin film electroluminescent element of the present invention has various configurations, but basically, it is composed of a plurality of organic compound layers and a pair of counter electrodes sandwiching the layers, and specifically, , Substrate / anode / hole injection layer / emission layer / cathode (FIG. 1 (1)), substrate / anode / emission layer / electron injection layer / cathode (FIG. 1 (2)), substrate / anode / hole injection layer / Emission layer / electron injection layer / cathode (FIG. 1 (3)) and the like, but the present invention is not necessarily limited to this structure, and each of the emission layer, the hole injection layer and the electron injection layer is provided. A plurality of layers may be provided, a hole injection layer / a light emitting layer, a light emitting layer / an electron injection layer, and a hole injection layer / a light emitting layer / an electron injection layer may be repeatedly laminated in each layer. Between the mixed layer of electron injection material and light emitting material, hole injection layer and emission layer No problem be provided other layers in the mixed layer is provided or also each of the hole injecting material and a light emitting material between the layers.

The light emitting layer is formed by a vapor deposition method, a spin coating method, a casting method or the like, and its film thickness is preferably 10 to 1000 nm, more preferably 20 to 150 nm. The hole injection layer is formed by a vapor deposition method, a spin coating method, a casting method or the like, and the film thickness thereof is preferably 10 to 1000 nm, more preferably 40 to 20 nm.
It is 0 nm. The electron injection layer is formed by a vapor deposition method, a spin coating method, a casting method or the like, and its film thickness is preferably 10 to 1000 nm, more preferably 30 to 200 nm.

The substrate 1 is made of soda glass, non-fluorescent glass,
Glass plates such as phosphoric acid glass, boric acid glass, quartz, acrylic resin, styrene resin, polycarbonate resin, epoxy resin, polyethylene, polyester, silicone resin and other plastic plates and plastic films, alumina and other metal plates And a metal foil or the like is used.

The anode 2 preferably has a work function larger than 4 eV, such as carbon, aluminum, vanadium,
Metals such as iron, cobalt, nickel, chromium, copper, zinc, tungsten, silver, tin, platinum and gold and alloys thereof, tin oxide such as zinc oxide, indium oxide, ITO and NESA or indium tin oxide-based composites Compounds, compounds such as copper iodide, mixtures of oxides and metals such as ZnO: Al, SnO ₂ : Sb, and conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline are used. The film thickness is preferably 10 to 1000 nm,
More preferably, it is 10 to 200 nm.

The cathode 3 preferably has a work function smaller than 4 eV, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, aluminum, silver, tin and lead. Metals and alloys thereof, aluminum / aluminum oxide composites and the like are used. The film thickness is preferably 10 to 1000 nm,
More preferably, it is 10 to 900 nm.

When light is taken out from the electrode, at least one of the anode 2 and the cathode 3 is transparent or semitransparent with a transmittance of 10% or more, and only the anode 2 is transparent or semitransparent with a transmittance of 10% or more. When it is transparent, the substrate 1 is also preferably transparent or semi-transparent.

Specific examples of the luminescent substance used in the luminescent layer 4 include oxinoid compounds (JP-A-63-295695 and JP-A-2-155) in addition to the organic compound represented by the above general formula.
95, No. 2-66873, etc.), perylene compounds (“Soluble Perylene Fluorescent Dyes with Photo
stability, vol.115, P2927 (1982) "," Jpn. Journal of A
pplied Physics, vol.27, No2, L269 (1988) "," Bull.Che
m.Soc.Jpn.vol.25, L411 (1952) ", European Patent 553,353A1
No. 55, No. 55-36849, No. 57-51781, No. 2-66873
Nos. 2-196885, 2-288188, 3-791, etc.) and coumarin compounds (JP-A-57-51781, JP-A-2-66873, 3-792, etc.). Described), azacoumarin compounds (described in JP-A-3-792, etc.), oxazole compounds (US Pat. No. 3,257,203, JP-A-3-93763).
No., No. 3-162482, No. 2-220396, etc.),
Oxadiazole compounds (described in US Pat. No. 3,189,447, JP-A-2-216791, etc.), perinone compounds (described in JP-A-2-88689, JP-A-2-289676, etc.), pyrrolopyrrole compounds (special Those described in Kaihei 2-296891), naphthalene compounds (JP-A-57-51781, JP-A-2-2)
55789, 3-162485, etc.), anthracene compounds (JP-A-56-46234, JP-A-57-51781, JP-A-5-51781)
2-66873, 3-162485, etc.), fluorene compounds (described in JP-A-54-110837, JP-A-3-162485, etc.), fluoranthene compounds (JP-A-3-16)
2485), a tetracene compound (JP
3-162485, etc.), pyrene compounds (JP
57-51781, JP-A-3-162485, JP-A-3-502333, etc.), coronene compound (JP-A-3-162485, etc.), quinolone compound, and azaquinolone compound (JP-A-3-261485). 162483, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. No. 3,180,729;
4,278,746, JP-A-55-88064, 55-88065, 49-
105537, 55-51086, 56-80051, 56-88141
No. 57-45545, No. 54-112637, No. 55-74546, those described in JP-A-2-220394, 3-162486, etc.), rhodamine compounds (JP-A-2-66873, JP-A-2-66873, 3-188189 etc.), chrysene compounds (JP-A-57-51781,
JP-A-3-502333, etc.), phenanthrene compound (JP-A-57-51781, etc.), cyclopentadiene compound (JP-A-2-289675, etc.), stilbene compound ( U.S. Pat. No. 4,356,429, JP-A-57-51781, 61-210363, 61-228451, 61-1.
No. 4642, No. 61-72255, No. 62-47646, No. 62-36674,
62-10652, 62-30255, 60-934454, 60-94
No. 462, No. 60-174749, No. 60-175052, No. 63-149652
JP-A Nos. 1-173034, 1-200262, 1-245087, etc.), diphenylquinone compounds ("Polyme
r Preprints, Japan, vol.37, p681 (1988) ", JP-A-3-152
No. 184) and styryl compounds (JP-A 1-2
45087, 2-209988, 2-222484, 2-247278, etc.), butadiene compound (US Pat.
6,429, those described in JP-A-57-51781, etc.), dicyanomethylenepyran compounds (JP-A-2-66873, JP-A-3-162)
481), dicyanomethylene thiopyran compound (described in JP-A-2-66873, JP-A-3-162481, etc.), fluorescein compound (described in JP-A-2-66873, etc.), Pyrylium compound (JP-A-2-66873
, Etc.), thiapyrylium compounds (JP
2-66873 etc.), selenapyrylium compound (described in JP-A-2-66873 etc.), telluropyrylium compound (described in JP-A-2-66873 etc.),
Aromatic adadiene compounds (described in JP-A-2-220393, etc.), oligophenylene compounds (JP-A-3-62484)
, Etc.), thioxanthene compounds (JP
3-177486), anthracene compound (described in JP-A-3-178942), cyanine compound (described in JP-A-2-66873), acridine compound (JP-A-57). -51781), metal chain of 8-hydroxyquinoline compound (Japanese Patent Laid-Open No. 2-8287,
2-8290), metal chains of 2,2'-bipyridine compounds (such as those described in JP-A Nos. 2-8288 and 2-8289), Schiff salts and Group III metals Chain (Japanese Patent Laid-Open No. 1-29749
No. 0, etc.), oxine metal chain (Japanese Patent Laid-Open No. 3-1
76993, etc.), rare earth chain (Japanese Patent Laid-Open No. 1-256)
No. 584, No. 1-282291, etc.) can be used.

Preferred examples of these compounds include the following.

[0077]

[Chemical 41]

[0078]

[Chemical 42]

[0079]

[Chemical 43]

[0080]

[Chemical 44]

[0081]

[Chemical 45]

[0082]

[Chemical 46]

[0083]

[Chemical 47]

[0084]

[Chemical 48]

[0085]

[Chemical 49]

[0086]

[Chemical 50]

[0087]

[Chemical 51]

[0088]

[Chemical 52]

[0089]

[Chemical 53]

[0090]

[Chemical 54]

In the above representative examples, each R is independently derived from a hydrogen atom, a halogen atom, a substituted or unsubstituted five groups described below; an alkyl group, a heterocyclic group, an aryl group and an unsaturated chain hydrocarbon. Monovalent group, group containing two or more nitrogen atoms, or styryl group, anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl A group, an acyl group, an aryloxy group, an aralkyl group, an acylamino group, an acyloxy group, a hydroxyl group, a cyano group, a nitro group, a sulfo group and a sulfonium group, X ⁻ represents an anion, and Y represents a chalcogen atom.

These are only specific examples and representative examples shown for the purpose of explanation, and do not limit the scope of the claims of the present invention.

Specific examples of the hole-injecting compound having a hole-transporting ability used in the hole-injecting layer 5 include triazole derivatives (described in US Pat. No. 3,112,197) in addition to the organic compound represented by the above general formula. , Oxadiazole derivatives (described in US Pat. No. 3,189,447, etc.), imidazole derivatives (described in Japanese Patent Publication No. 37-16096, etc.), polyarylalkane derivatives (US Pat.
615,402, 3,820,989, 3,542,544, Japanese Patent Publication No. 45-
555, 51-10983, JP-A-51-93224, 55-17105
No. 56, No. 56-4148, No. 55-108667, No. 56-36656, No. 55.
-156953), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729 and 4,278,746).
No. 55/88064, No. 55-88065, No. 49-105537
No. 55, No. 55-51086, No. 56-80051, No. 56-88141, No. 57.
-45545, 54-112637, 55-74546, etc.), phenylenediamine derivatives (US Pat. No. 3,615,40)
No. 4, Japanese Patent Publication No. 51-10105, No. 46-3712, No. 47-25336,
JP-A-54-53435, JP-A-54-110536, JP-A-54-119925, etc.), arylamine derivatives (US Pat. No. 3,56,56)
7,450, 3,180,703, 3,240,597, 3,658,520
Issue 4,232,103, Issue 4,175,961, Issue 4,012,376,
JP-B-49-35702, JP-B-39-27577, JP-A-55-144250
Nos. 56-223437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivatives (US Pat. No. 3,52)
6,501), oxazole derivatives (described in US Pat. No. 3,257,203), styrylanthracene derivatives (described in JP-A-56-46234), fluorenone derivatives (JP-A-54-110837). , Hydrazone derivatives (US Pat. No. 3,717,462)
JP, 54-59143, 55-52063, 55-52064,
55-46760, 55-85495, 57-148749, JP-A-3.
-136059, 3-138654, etc.), stilbene derivatives (JP-A 61-210363, 61-228451, 61)
-14642, 61-72255, 62-47646, 62-36674
No. 62, No. 62-10652, No. 62-30255, No. 60-934454, No. 6
0-94462, 60-174749, 60-175052, 63-1496
52, those described in JP-A Nos. 1-173034 and 1-200262, etc.), porphyrin compounds (US Pat. No. 3,935,031,
4,356,429, JP-A-63-295695, JP-A-2-12795, etc.), aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A-53-27).
033, 54-58445, 54-149634, 54-64299,
55-79450, 55-144250, 56-119132, 61-2
No. 95558, No. 61-98353, No. 63-295695, JP-A 1-2433
Nos. 93, 3-111485, etc.), butadiene compounds (those described in JP-A-3-111484, etc.), polystyrene derivatives (those described in JP-A-3-95291, etc.), hydrazone derivatives ( (Such as those described in JP-A-3-137187), triphenylmethane derivatives, tetraphenylbenzine derivatives (compounds described in JP-A-3-54289, etc.) and the like can be used, but porphyrin compounds are particularly preferable. , Aromatic tertiary amine compounds and styrylamine compounds. As typical examples of these compounds,
The following are listed.

[0094]

[Chemical 55]

[0095]

[Chemical 56]

[0096]

[Chemical 57]

[0097]

[Chemical 58]

[0098]

[Chemical 59]

[0099]

[Chemical 60]

[0100]

[Chemical formula 61]

[0101]

[Chemical formula 62]

[0102]

[Chemical 63]

In the above representative examples, each R is independently derived from a hydrogen atom, a halogen atom, a substituted or unsubstituted five groups described below; an alkyl group, a heterocyclic group, an aryl group, and an unsaturated chain hydrocarbon. Monovalent group, group containing two or more nitrogen atoms, or styryl group, anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl Group, acyl group, aryloxyl group, aralkyl group, acylamino group, acyloxyl group, hydroxyl group, cyano group, nitro group, sulfo group and sulfonium group, n represents an integer of 1 or more, and M represents a metal atom. Represent

These are only specific examples and representative examples shown for the purpose of explanation, and do not limit the scope of the claims of the present invention.

Specific examples of the electron injecting compound having an electron transporting ability used in the electron injecting layer 6 include, in addition to the organic compound represented by the above general formula, a nitro-substituted fluorenone derivative, a thiopyrandioxide derivative, a diphequinone derivative (“Polymer Preprints”). , Japan, vol.37, No3, P681,
(1988) ", JP-A-3-152184, etc.), perylene tetracarboxyl derivative (" Jpn. Journal of App
lied Physics, vol.27, No2, L269 (1988) '' Bull.Chem.So
c. Jpn., vol. 25, L411 (1952) ”, etc.) Anthraquinodimethane derivative (JP-A-57-149259, 58-5545)
No. 0, No. 61-225151, No. 61-133750, No. 63-104061, etc.), phenylenylidene methane derivative (JP-A-60-69657, No. 61-143764, No. 61- No. 148159, etc.), anthrone derivative (JP-A-61-225151)
No. 61-233750), oxadiazole derivatives (such as those described in JP-A-3-79692), perinone derivatives (such as those described in JP-A-2-289676),
Compounds such as quinoline complex derivatives can be used. The following are typical examples of these compounds.

[0106]

[Chemical 64]

[0107]

[Chemical 65]

[0108]

[Chemical 66]

[0109]

[Chemical 67]

In the above representative examples, each R is independently a hydrogen atom, a halogen atom, an alkyl group having or not having a substituent, a heterocyclic group having or not having a substituent, an aryl having or not having a substituent. Group, monovalent group derived from unsaturated chain hydrocarbon with or without substituent, group containing two or more nitrogen atoms with or without substituent, styryl group, anisyl group, amino group, alkylamino Group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl group, acyl group, aryloxyl group, aralkyl group, acylamino group, acyloxyl group, hydroxyl group, cyano group, nitro group, It represents a sulfo group and a sulfonium group, and M represents a metal atom.

These are only specific examples and representative examples shown for the purpose of explanation, and do not limit the scope of the claims of the present invention.

[0112]

EXAMPLES The present invention will be described in detail with reference to examples.

Example 1 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the exemplified compound (II-72) styryl compound was put into a tungsten board (SF208 manufactured by Nippon Bucks Metal Co., Ltd.), and under a vacuum condition of 8.0 × 10 ⁻⁷ Torr.
Vacuum deposition was performed at a film formation rate of 0.2 nm / sec to form a hole injection layer of 81 nm.

Next, the compound (I-1) was placed in a molybdenum boat (SS-1-9, manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was added. A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the organic thin film electroluminescence device thus obtained, and a 17 V DC voltage was applied to obtain an emission of maximum brightness of 63.9 cd / m ² . Further, when continuous lighting was performed by applying a DC voltage of 17 V in a dry nitrogen gas atmosphere at a temperature of 23 ° C., the time required to reduce the luminance by half was 1589 hours.

Example 2 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the styryl compound of Exemplified Compound (II-19) was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 79 nm.

Then, the compound (I-1) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was added. A 64 nm light emitting layer was laminated and deposited at a film forming rate of sec.

Further, Mg: Ag (alloy of 10: 1 atomic ratio) was vacuum-deposited on this to 500 nm without breaking vacuum conditions,
A cathode was formed.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and a voltage of 18 V DC was applied to obtain light emission with a maximum brightness of 58.0 cd / m ² .

Further, the temperature was 23 ° C., and 18 V under a dry nitrogen gas atmosphere.
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1432 hours.

Example 3 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape, and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the compound (II-48) styryl compound was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.), and the film formation rate was 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. Vacuum deposition was performed to form an 80 nm hole injection layer.

[0126] Next, the compound without breaking the vacuum conditions (I-1) put in a molybdenum boat (Japan Bucks made of metal, Ltd. SS-1-9), 0.2nm under vacuum conditions of 8.0 × 10 ^-7 Torr / A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, on top of this, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and a 19 V DC voltage was applied, whereby light emission with a maximum brightness of 57.7 cd / m ² was obtained.

Further, the temperature was 23 V and 19 V in a dry nitrogen gas atmosphere.
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to decrease by half was 1413 hours.

Example 4 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape, and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the compound (II-91) styryl compound was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.), and the film formation rate was 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. Vacuum deposition was performed to form an 80 nm hole injection layer.

Then, the compound (I-1) was placed in a molybdenum boat (SS-1-9, manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / under a vacuum condition of 8.0 × 10 ⁻⁷ Toor. A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, on top of this, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescent element, and by applying a DC voltage of 19 V, light emission with a maximum brightness of 57.6 cd / m ² was obtained.

Further, the temperature was 23 V and 19 V in a dry nitrogen gas atmosphere.
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1487 hours.

Example 5 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the styryl compound of Exemplified Compound (II-14) was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 80 nm.

[0138] Next, the compound without breaking the vacuum conditions (I-1) put in a molybdenum boat (Japan Bucks made of metal, Ltd. SS-1-9), 0.2nm under vacuum conditions of 8.0 × 10 ^-7 Torr / A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, on top of this, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescent element, and a 19 V DC voltage was applied, whereby light emission with a maximum luminance of 54.7 cd / m ² was obtained.

Also, at a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 19 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1404 hours.

Example 6 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the styryl compound of Exemplified Compound (II-84) was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 81 nm.

[0144] Next, the compound without breaking the vacuum conditions (I-1) put in a molybdenum boat (Japan Bucks made of metal, Ltd. SS-1-9), 0.2nm under vacuum conditions of 8.0 × 10 ^-7 Torr / A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, on top of this, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and a voltage of 18 V was applied to it to obtain light emission with a maximum brightness of 60.7 cd / m ² .

At a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 17 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1532 hours.

Example 7 A substrate (P110E-H-PS, manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the exemplified compound (II-72) styryl compound was put on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 82 nm.

Next, the compound (I-1) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / cm under a vacuum condition of 8.0 × 10 ^-7 Torr. A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, on this, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and a voltage of 18 V was applied to it to obtain light emission with a maximum brightness of 55.1 cd / m ² .

Also, the temperature was 18 V in a dry nitrogen gas atmosphere at 23 ° C.
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to decrease by half was 1529 hours.

Example 8 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, a styryl compound of Exemplified Compound (II-27) was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 81 nm.

Next, the compound (I-28) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was applied. A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

[0157] Furthermore, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and by applying a DC voltage of 22 V, light emission with a maximum brightness of 48.3 cd / m ² was obtained.

At a temperature of 23 ° C. and a dry nitrogen gas atmosphere of 22 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1652 hours.

Example 9 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the exemplified compound (II-72) styryl compound was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 80 nm.

Next, the compound (I-95) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was added. A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, without breaking the vacuum condition, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescent element, and a 15 V DC voltage was applied, whereby light emission with a maximum luminance of 52.4 cd / m ² was obtained.

At a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 15 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1552 hours.

Example 10 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape, and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Then, the exemplified compound (II-72) was applied to this substrate by a tungsten boat (S manufactured by Nippon Bucks Metal Co., Ltd.).
F208) and 0.2 nm / se under vacuum condition of 8.0 × 10 ^-7 Torr
Vacuum deposition was performed at a film formation rate of c to form a hole injection layer of 80 nm.

Next, the compound (I-96) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was applied. A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Furthermore, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power supply was connected to the thus obtained organic thin film electroluminescence device and a 19 V DC voltage was applied to obtain light emission with a maximum brightness of 50.8 cd / m ² .

Also, at a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 19 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to decrease by half was 1529 hours.

Example 11 A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then polished with water using an alumina abrasive. went. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Then, the exemplified compound (II-72) was applied to this substrate by a tungsten boat (S manufactured by Nippon Bucks Metal Co., Ltd.).
F208) and 0.2 nm / se under vacuum condition of 8.0 × 10 ^-7 Torr
Vacuum deposition was performed at a film formation rate of c to form an 81 nm hole injection layer.

Then, the compound (I-42) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. A 63 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

[0175] Furthermore, without breaking the vacuum condition, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and a 20 V DC voltage was applied, whereby light emission with a maximum brightness of 50.1 cd / m ² was obtained.

At a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 20 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to decrease by half was 1501 hours.

Comparative Example (1) A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then treated with water using an alumina abrasive. Polished. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, on this substrate, the exemplified compound (p-1);
1,1-bis (4-di-p-tolylaminophenyl) cyclohexane was placed in a tungsten boat (SF208 made by Nippon Bucks Metal Co., Ltd.) under a vacuum condition of 8.0 × 10 ⁻⁷ Torr.
Vacuum deposition was performed at a film formation rate of 2 nm / sec to form a hole injection layer of 80 nm.

Next, the following compound (L-1-1) tris (8-hydroxyquinoline) aluminum was placed in a molybden boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum conditions, and 8.0 × 10 ^A 64 nm light emitting layer was laminated and deposited at a deposition rate of 0.2 nm / sec under a vacuum condition of ^-7 Torr.

[0181]

[Chemical 68]

Furthermore, without breaking the vacuum condition, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescent element, and by applying a DC voltage of 24 V, light emission with a maximum luminance of 28.3 cd / m ² was obtained.

At a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 24 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to decrease by half was 630 hours.

Comparative Example (2) After patterning a substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) in which ITO was deposited to a thickness of 150 nm on a glass as an anode into a desired shape, an alumina abrasive was used together with water. Polished. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the exemplary compound (II-72) styryl compound was put into this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.) to form a film at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 81 nm.

Then, the compound (L-1-1) tris (8-hydroxyquinoline) aluminum was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum conditions, and 8.0 × 10 ^{− A} 64 nm light emitting layer was laminated and deposited at a film forming rate of 0.2 nm / sec under a vacuum condition of ⁷ Torr.

Furthermore, on top of this, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescence device, and by applying a DC voltage of 23 V, light emission with a maximum brightness of 43.2 cd / m ² was obtained.

At a temperature of 23 ° C. in a dry nitrogen gas atmosphere, 23 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 932 hours.

Comparative Example (3) A substrate (P110E-H-PS manufactured by Nippon Sheet Glass Co., Ltd.) having a 150 nm ITO film formed on glass as an anode was patterned into a desired shape and then treated with an alumina abrasive together with water. Polished. After washing with water, ultrasonic washing with water was performed twice for 10 minutes, ultrasonic washing with acetone for 10 minutes twice, and ultrasonic washing with isopropyl alcohol for 10 minutes twice, followed by hot air drying at 90 ° C.

Next, the exemplified compound (p-2) stilbene derivative was placed on this substrate in a tungsten boat (SF208 manufactured by Nippon Bucks Metal Co., Ltd.), and a film was formed at 0.2 nm / sec under a vacuum condition of 8.0 × 10 ⁻⁷ Torr. It vacuum-deposited at a rate to form a hole injection layer of 79 nm.

Next, the compound (I-1) was placed in a molybdenum boat (SS-1-9, manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / 8.0 × 10 ⁻⁷ Torr vacuum condition was applied. A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

On top of this, without breaking vacuum conditions, M
g: Ag (10: 1 atomic ratio alloy) was vacuum-deposited at 500 nm to form a cathode.

An external power source was connected to the thus obtained organic thin film electroluminescent element, and a 20 V DC voltage was applied, whereby light emission with a maximum brightness of 44.1 cd / m ² was obtained.

At a temperature of 23 ° C. under a dry nitrogen gas atmosphere, 20 V
When continuous lighting was performed by applying a DC voltage, the time required for the luminance to halve was 1240 hours.

[0197]

By using the specific organic compound according to the present invention, it is possible to obtain an organic thin film electroluminescent device which is sufficiently practical for emission intensity and durability.

[Brief description of drawings]

FIG. 1 (1) to (3) are cross-sectional views of an organic thin film electroluminescent element according to an embodiment of the present invention.

[Explanation of symbols]

 1 substrate 2 anode 3 cathode 4 light emitting layer 5 hole injection layer 6 electron injection layer

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 12, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

[0012]

DETAILED DESCRIPTION OF THE INVENTION Residue ( Z1 ) of the general formula [I]
( Z5 ) and the halogen atom represented by the general formula [II] include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.
Rogen atom ; Substituted or unsubstituted alkyl group is an alkyl group such as methyl group, ethyl group, propyl group, butyl group, cyclohexyl group; Monovalent group derived from substituted or unsubstituted unsaturated chain hydrocarbon vinyl group as, 1-propenyl, a Lil group, isopropenyl group, 1-
Monovalent groups derived from unsaturated chain hydrocarbons such as butenyl group, 2-butenyl group, 2-pentenyl group, ethynyl group;
Examples of the substituted or unsubstituted heterocyclic group include piperidyl group, piperidino group, pyrrolyl group, furyl group, cenyl group, imidazolyl group, pyrazolyl group, triazolyl group,
Pyridyl group, a thiazolyl group, a pyridazinyl group, a monovalent group formed from pyridone, morpholinyl group, morpholino group, oxazolyl group, isoxazolyl group, isothiazolyl group, pyrimidinyl group, pyrazinyl group, pyranyl group, benzimidazolyl group, benzothiazolyl group, Heterocyclic groups such as oxazolyl group and quinolyl group; substituted or unsubstituted aryl groups include phenyl group, naphthyl group,
Aryl groups such as anthonyl group, xylyl group, biphenyl group, phenanthryl group; substituted or unsubstituted nitrogen 2
As the group containing at least one atom, a group containing at least two nitrogen atoms such as azo group, phenylazo group, naphthyrazo group, hydranizo group, hydrazo group, azoxy group, azido group, diazoamino group, amidino group, ureylene group, guanidino group; alkoxyl Alkoxyl groups such as methoxyl group, ethoxyl group, propoxyl group, butoxyl group, pentyloxyl group, hexyloxyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, etc. as alkoxycarbonyl group; Aminocarbonyl groups such as anilinocarbonyl group, dimethylaminocarbonyl group, larvamoyl group, and alanyl group; aryloxycarbonyl groups such as naphthyloxycarbonyl group and xylyloxycarbonyl group. Aryloxycarbonyl groups such as bonyl group and phenoxycarbonyl group; acyl groups as formyl group, acetyl group, propionyl group, butyryl group, pareryl group, oialuminoyl group, stearoyl group, oleoyl group, benzoyl group, trioyl group, salicyloyl group Acyl groups such as cinnamoyl group, naphthoyl group, phthaloyl group, oxalyl group, malonyl group, succinyl group and furoyl group; aryloxyl groups such as phenoxy group and tolyloxy group; aryloxyl groups such as aralkyl group, benzyl group and phenethyl group Groups such as aralkyl groups; acylamino groups such as acetylamino groups, propionylamino groups, butyrylamino groups such as acylamino groups; acyloxyl groups such as acetyloxy groups, propionyloxy groups, butyryl An acyloxyl group such as alkoxy group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

The above-mentioned substituents include hydrogen atom, halogen atom, alkyl group such as methyl group, ethyl group, propyl group, butyl group and cyclohexyl group, vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-
Monovalent groups derived from unsaturated chain hydrocarbons such as butenyl group, 2-pentenyl group, ethynyl group, piperidyl group,
Piperidino group, pyrrolyl group, furyl group, cenyl group,
Imidazolyl group, a pyrazolyl group, a triazolyl group, a pyridyl group, a thiazolyl group, a pyridazinyl group, a monovalent group formed from pyridone, morpholinyl group, Moruho Reno group, oxazolyl group, isoxazolyl group, isothiazolyl group, pyrimidinyl group, pyrazinyl group, pyranyl group , Heterocyclic groups such as benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, quinolyl group, phenyl group, naphthyl group, anthonyl group, aryl groups such as xylyl group, biphenyl group, phenanthryl group, azo group, phenylazo group, Groups containing 2 or more nitrogen atoms such as naphthyrazo group, hydranizo group, hydrazo group, azoxy group, azido group, diazoamino group, amidino group, ureylene group, guanidino group, styryl group, anisyl group, amino group, alkylamino group, dialkyl group. Group, methoxyl group, ethoxyl group, propoxyl group, butoxyl group, pentyloxyl group, hexyloxyl group and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and other alkoxycarbonyl groups, anilinocarbonyl group, Aminocarbonyl groups such as dimethylaminocarbonyl group, larvamoyl group, alanyl group, naphthyloxycarbonyl group, xylyloxycarbonyl group, aryloxycarbonyl group such as phenoxycarbonyl group, carboxyl group, formyl group, acetyl group, propionyl group, butyryl Group, pareryl group, oaluminoyl group, stearoyl group, oleoyl group, benzoyl group, trioyl group, salicyloyl group, cinnamoyl group, naphthoyl group, phthaloyl group, oxalyl group, malo Group such as acyl group, succinyl group and furoyl group, aryloxy group such as phenoxy group and tolyloxy group, aralkyl group such as benzyl group and phenethyl group, acylamino group such as acetylamino group, propionylamino group and butyrylamino group, acetyl It represents an acyloxyl group such as an oxy group, a propionyloxy group and a butyryloxy group, a hydroxyl group, a cyano group, a nitro group, a sulfo group or a sulfonium group.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Chemical formula 26]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

[Chemical 27]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

[0040]

[Chemical 28]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

[Chemical 37]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051]

[Chemical Formula 39]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

Synthesis Example 1 Chloranil (21 g; mp287 ° C.), maleic anhydride (150 g; mp55.5 ° C.) and perylene (10 g; mp280) were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel.
(° C) is thoroughly crushed and mixed, and while heating,
Stir for 10 minutes. Then, warmed xylene (200 ml) was added from the dropping funnel, stirred and boiled for 1 hour, and hot filtered. The reddish brown needle-like crystals separated by hot filtration were washed with xylene and further thoroughly washed with ether to obtain reddish-brown needle-like crystals. The obtained reddish brown needle crystals were sublimated for 4 hours and a half at 300 ° C and 10 ^-4 mmHg using a vacuum sublimation device, and the sublimation residue was further used at 400 ° C and 10 ^-4 mmHg for 6 hours using a vacuum sublimation device. By processing, glossy reddish brown needle crystals (I-2
8) was obtained.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

The phosphorus compound represented by the general formula [III] can be easily prepared by heating the corresponding halomethyl compound and triarylphosphine or trialkylphosphine or trialkylphosphite directly or in a solvent such as toluene or xylene. Can be manufactured.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

[0085]

[Chemical 49]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

[0086]

[Chemical 50]

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

[0106]

[Chemical 64]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0117

[Correction method] Change

[Correction content]

An external power source was connected to the thus obtained organic thin film electroluminescent element, and a 17 V DC voltage was applied, whereby light emission with a maximum luminance of 63.9 cd / m ² was obtained. Further, when continuous lighting was performed by applying a DC voltage of 17 V in a dry nitrogen gas atmosphere at a temperature of 23 ° C., the time required to reduce the luminance by half was 1589 hours.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0146

[Correction method] Change

[Correction content]

An external power source was connected to the thus obtained organic thin film electroluminescent element, and a 17 V DC voltage was applied, whereby light emission with a maximum luminance of 60.7 cd / m ² was obtained.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0150

[Correction method] Change

[Correction content]

Then, the compound (I- 2 ) was placed in a molybdenum boat (SS-1-9 manufactured by Nippon Bucks Metal Co., Ltd.) without breaking the vacuum condition, and 0.2 nm / 0.2 nm / vacuum condition was obtained under a vacuum condition of 8.0 × 10 ^-7 Torr. A 62 nm light emitting layer was laminated and vapor deposited at a film formation rate of sec.

Claims (2)

[Claims] 1. An electroluminescent device comprising a pair of counter electrodes and a plurality of organic compound layers sandwiched therebetween, a layer containing an organic compound represented by the following general formula [I], and a general formula: An organic thin film electroluminescent device, comprising at least one layer containing a styryl compound represented by [II]. [Chemical 1] [In residue (Z1) to (Z4) of residue Z of general formula [I], R ₁ to
R _{11 s} are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted five groups described below; an alkyl group, a monovalent group derived from an unsaturated chain hydrocarbon, a heterocyclic group, an aryl group, Group containing two or more nitrogen atoms, or styryl group, anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl group, acyl group, aryloxyl Group, aralkyl group, acylamino group, acyloxyl group, hydroxyl group, cyano group, nitro group, sulfo group, sulfonium group, R
₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₆ and R ₇ , R ₇ and R ₈ , R
₈ and R ₉ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure. Further, X in the above formula (Z5) represents a substituted or unsubstituted heterocycle. ] [Chemical 2] [In the above general formula [II], R ₁₂ and R ₁₃ are each independently a hydrogen atom, a substituted or unsubstituted four groups described below; an alkyl group, a heterocyclic group, an aryl group, an unsaturated chain hydrocarbon. R ₁₂ and R ₁₃ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure. R ₁₄ is a substituted or unsubstituted three groups described below; an alkyl group, an aryl group, an alkoxy group or-{p (C ₆ H ₄ )}-CH = C {(-R ₁₂ ) (-R ₁₃ )} Represents
R ₁₂ and R ₁₃ are as defined above. R ₁₅ is a hydrogen atom,
Substituting or non-substituted, the following three groups; an alkyl group, an aryl group, and an alkoxy group. ] 2. The organic compound represented by the general formula [I] is used as a light emitting substance, and the styryl compound represented by the general formula [II] is used as a hole transporting substance.
2. The organic thin film electroluminescent element according to.