JP2002151268A - Organic compound, inorganic phosphor, color conversion filter, and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element of high intensity, long life and low power consumption by enabling to use an inorganic system phosphor as color conversion material for a through the use of an organic compound emitting light in bluish purple color as a light-emitting layer. SOLUTION: With the electroluminescent element provided with a negative electrode, a positive electrode and a light-emitting layer, the light-emitting layer has a band gap pf 2.96 eV to 3.80 eV, contains at least a kind of organic compound with molecular weight of 600 to 2,000, and the element emits light in purplish blue or bluish purple of CIE chromaticity coordinates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organic electroluminescence (hereinafter sometimes abbreviated as organic EL).
Elements and organic electroluminescent element materials, specifically, organic electroluminescent elements and organic electroluminescent element materials suitably used in consumer or industrial display devices such as light-emitting multi-color or full-color displays and display panels It is about.

[0002]

2. Description of the Related Art Electroluminescent displays (ELD) are used as light-emitting electronic display devices.
There is. ELD components include inorganic electroluminescent elements and organic electroluminescent elements. Inorganic electroluminescence elements have been used as flat light sources, but high voltage AC is required to drive the light emitting elements. An organic electroluminescence element has a configuration in which a light-emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. Electrons and holes are injected into the light-emitting layer and recombination causes exciton (exciton) to be generated. An element that emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated and emits light at a voltage of about several V to several tens of volts. Because of this, it is rich in viewing angle, has high visibility, and is a thin-film type completely solid-state device, which is attracting attention from the viewpoint of space saving, portability, and the like.

[0003] However, organic EL devices for practical use in the future include more efficient and higher brightness with lower power consumption.
There is a demand for the development of an organic EL device that emits light for a long life.
Further, development of a low-cost organic EL element is desired.
Until now, various organic EL devices have been reported.

A monochrome display using an organic EL element has been put to practical use as a green monochrome display, and is a simple matrix structure panel having 256 × 64 pixels mounted on a vehicle-mounted FM character multiplexing receiver. (H.Nakada and T.Tohma: Ext. Abstr. 7th Int. Wor
kshopInorganic and Organic Electroluminescence p.3
85 (1996)). In contrast to a monochrome display, a so-called area color display that expresses several colors for each specific area of the display, blue, green,
Colors such as yellow and orange have been released (May 7, 1999, Dempa Shimbun and others), but purple blue and blue purple have not been developed.

Compounds that emit blue-violet light include 61st
Proceedings of the Japan Society of Applied Physics (2000.9
(Hokkaido Institute of Technology) discloses that polysilane light-emitting diodes are used for organic EL devices. However, the light-emitting life of polysilane light-emitting diodes is short, and the brightness tends to be small due to this. It was not a level that could be changed.

[0006] However, in general, the organic phosphor deteriorates and decomposes depending on the type of the medium such as a solvent or a resin, so that the emission intensity is reduced. In addition, under strong light of about 100,000 lux, most of the light is decomposed in a few minutes to several hours, and there is no organic phosphor that can withstand long-term storage.

Various reports have been made on compounds contained in the light emitting layer. Compounds contained in the light emitting layer are roughly classified into low molecular weight compounds and high molecular weight compounds. In small molecule systems,
For example, Japanese Patent Application Laid-Open No. 3-12897 discloses an organic electroluminescent device containing p-quarterphenyl, but has a low emission luminance and is not sufficient.

In Japanese Patent Application Laid-Open Nos. 10-92578 and 10-106749, compounds in which benzimidazole is incorporated in the molecule are studied, but the light emission luminance is not sufficient even with these compounds. Japanese Patent Application Laid-Open No. 6-84531 discloses a fluorescent material comprising a pyrazoline compound, but is insufficient from the viewpoint of thermal stability to be used as a material for an organic EL device.

[0009] The low molecular weight luminescent materials as described above have poor thermal stability if their molecular weights are small, so they are easily decomposed and their luminescence lifetime is not sufficient. On the other hand, for polymer materials,
There are polysilane compounds disclosed in JP-A-26159 and polycarbonates disclosed in JP-A-5-247559. These are generally unstable and have a short emission life, are difficult to emit at room temperature, and have low luminous efficiency.

Further, a very small amount (1) is contained in the light emitting layer of the organic EL device.
There is known a technique (doping) of mixing a fluorescent material (0 mol% or less) to convert light emitted from the light emitting layer into light emitted from the fluorescent material. The advantages of the doping technique of adding a small amount of fluorescent material include an improvement in luminous efficiency and multicolor coloring. Specific doping techniques include the following.

In Japanese Patent No. 3093796, a small amount of a fluorescent dopant is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative, thereby improving the luminous efficiency and extending the life of the device.

Further, an element having an organic light emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of a fluorescent dopant is doped in the host compound (Japanese Patent Laid-Open No.
No. 2,264,692), an element having an organic light emitting layer doped with a quinacridone dye using an 8-hydroxyquinoline aluminum complex as a host compound.
No. 5190).

However, in such conventional doping, it is known that the host compound absorbs blue, green, yellow, and orange light emitted from the host compound and emits longer-wavelength fluorescent light. There has been no known host compound that absorbs violet or violet blue fluorescent light and emits light of a longer wavelength.

Various reports have also been made on the color conversion layer of the organic EL device. As color conversion materials used in the color conversion layer, JP-A-3-52897, JP-A-9-245511, JP-A-5-245511
No. 258860 reports the use of an organic phosphor.

Further, when the above-mentioned organic phosphor is used for the color conversion layer, there is a drawback that an aggregate is easily formed due to interaction between molecules, and the emission wavelength becomes broad. It is also known that when the amount of the organic phosphor added is increased to increase the luminance, the association becomes more intense and concentration quenching occurs. As a result, even if the organic phosphor itself has a high quantum yield,
When used as an element, the luminance is greatly reduced, resulting in the compound not being able to achieve its full potential.

On the other hand, inorganic compounds generally have a long life. Further, since the inorganic compound has a sharp emission wavelength and does not form an aggregate, the quantum yield is higher than that of the organic phosphor, so that the color conversion efficiency is high. The inorganic compound is useful as a color conversion material used in the color conversion layer because the amount of the inorganic compound added and the power consumption can be reduced because the color conversion efficiency is high.

However, the inorganic compound has an excitation wavelength on the short wavelength side, and a blue light emitting material has a maximum emission wavelength on a longer wavelength side than the excitation wavelength of the inorganic compound, so that the inorganic compound emits light with high color conversion efficiency. I couldn't do that. Note that the quantum yield refers to a ratio of emitted photons to photons absorbed by a substance.

[0018]

As described above, there is a need for an organic EL device that has a long life, emits light with high luminance, consumes little power, and is low in cost as an organic electroluminescence device.

The present invention has been made in view of the above situation. The present invention is a novel organic compound that emits blue-violet or purple-blue light, emits light with high luminance and long life, an organic electroluminescent element that emits blue-violet or purple-blue light, an organic electroluminescent element that emits light with high luminance, Organic EL device with long life, organic EL device with low power consumption, organic EL device with low cost, inorganic phosphor with high color conversion efficiency, color conversion filter with high color conversion efficiency, high color conversion efficiency An object of the present invention is to provide at least one of an organic electroluminescence element and an organic electroluminescence element which is easy to manufacture.

[0020]

According to the present invention, the following arrangement and operation show the following effects. (1) An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer comprises:
Purplish Bl containing at least one organic compound having a band gap of 2.96 eV to 3.80 eV and a molecular weight of 600 to 2000, and having a CIE chromaticity coordinate.
ue (purple blue) or Blue Purple (purple purple)
Organic electroluminescent element that emits light.

(10) An organic electroluminescent device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVI).

[0022]

Embedded image

(Wherein, R _c1 , R _c2 and R _c3 each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ and X ₃ each represent —NR
_d- represents an oxygen atom or a sulfur atom. L ₁ , L ₂ ,
L ₃ represents a linking group having a π bond. R _d represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k
₁ , k ₂ and k ₃ represent an integer of 0 to 6. (11) An organic electroluminescent device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVII).

[0024]

Embedded image

(Wherein, R _e1 , R _e2 and R _e3 each independently represent a hydrogen atom or a substituent. X ₄ , X ₅ and X ₆ each represent —NR
_f- represents an oxygen atom or a sulfur atom. L ₄ ,
L ₅ and L ₆ represent a linking group having a π bond. R _f represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k ₄ , k ₅ and k ₆ represent an integer of 0 to 6. (12) An organic electroluminescent device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVIII).

[0026]

Embedded image

(Wherein, R _g1 , R _g2 and R _g3 each independently represent a hydrogen atom or a substituent. X ₇ , X ₈ and X ₉ each represent —NR
_h- represents an oxygen atom or a sulfur atom. L ₇ , L ₈ ,
L ₉ represents a linking group having a π bond. R _h represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k
₇ , k ₈ and k ₉ represent an integer of 0 to 6. (13) An organic electroluminescence device having a cathode, an anode, and a light-emitting layer, wherein the light-emitting layer contains an organic compound represented by the following general formula (XIX).

[0028]

Embedded image

(Where R _i1 , R _i2 , R _i3 , R _j1 , R _j2 ,
R _j3 each independently represents a hydrogen atom or a substituent.
X ₁₀ , X ₁₁ , and X ₁₂ represent —NR _k —, an oxygen atom, or a sulfur atom. R _k represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k _10, k
_11, k ₁₂ represents an integer of 0 to 6. (14) An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer has the following general formula (XX-1), (XX-2), (XX-3) or (XX-3). XX-4) At least one of the organic compounds represented by
Organic electroluminescent device containing seeds.

[0030]

Embedded image

(Where R _k1 , R _k2 , R _k3 , R _k4 , R _k5 ,
_{R k6, R k7, R k8} , R l1, R l2, R l3, R l4, R l5, R
_{l6, R l7, R l8,} R m1, R m2, R m3, R m4, R m5,
R _m6 , R _m7 , R _m8 , R _n1 , R _n2 , R _n3 , R _n4 , R _n5 , R
_n6 , _Rn7 and _Rn8 each independently represent a hydrogen atom or a substituent. (30) An organic compound represented by the following general formula (XVI).

[0032]

Embedded image

(Wherein, R _c1 , R _c2 and R _c3 each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ and X ₃ each represent —NR
_d- represents an oxygen atom or a sulfur atom. L ₁ , L ₂ ,
L ₃ represents a linking group having a π bond. R _d represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k
₁ , k ₂ and k ₃ represent an integer of 0 to 6. (31) An organic compound represented by the following general formula (XVII).

[0034]

Embedded image

(Wherein, R _e1 , R _e2 and R _e3 each independently represent a hydrogen atom or a substituent. X ₄ , X ₅ and X ₆ each represent —NR
_f- represents an oxygen atom or a sulfur atom. L ₄ ,
L ₅ and L ₆ represent a linking group having a π bond. R _f represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k ₄ , k ₅ and k ₆ represent an integer of 0 to 6. (32) An organic compound represented by the following general formula (XVIII).

[0036]

Embedded image

(Wherein, R _g1 , R _g2 , and R _g3 each independently represent a hydrogen atom or a substituent. X ₇ , X ₈ , and X ₉ represent —NR
_h- represents an oxygen atom or a sulfur atom. L ₇ , L ₈ ,
L ₉ represents a linking group having a π bond. R _h represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k
₇ , k ₈ and k ₉ represent an integer of 0 to 6. (33) An organic compound represented by the following general formula (XIX).

[0038]

Embedded image

(Where R _i1 , R _i2 , R _i3 , R _j1 , R _j2 ,
R _j3 each independently represents a hydrogen atom or a substituent.
X ₁₀ , X ₁₁ , and X ₁₂ represent —NR _k —, an oxygen atom, or a sulfur atom. R _k represents an alkyl group, an aryl group, a substituted alkyl group, or a substituted aryl group. k _10, k
_11, k ₁₂ represents an integer of 0 to 6. (34) The following general formulas (XX-1), (XX-2),
Organic compound represented by (XX-3) or (XX-4)

[0040]

Embedded image

(Where R _k1 , R _k2 , R _k3 , R _k4 , R _k5 ,
_{R k6, R k7, R k8} , R l1, R l2, R l3, R l4, R l5, R
_{l6, R l7, R l8,} R m1, R m2, R m3, R m4, R m5,
R _m6 , R _m7 , R _m8 , R _n1 , R _n2 , R _n3 , R _n4 , R _n5 , R
_n6 , _Rn7 and _Rn8 each independently represent a hydrogen atom or a substituent. (38) An inorganic phosphor represented by the following general formula (A).

Formula (A): M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2z is satisfied. n may be 0. (39) A color conversion filter comprising at least one compound represented by the following general formula (A).

General formula (A): M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2z is satisfied. n may be 0. (42) An organic electroluminescence device having a cathode, an anode, and a light-emitting layer, comprising an organic compound having a band gap of 2.96 eV to 3.80 eV, and a phosphor, and having a wavelength of 450 to 700 nm. An organic electroluminescent device having at least one maximum emission wavelength within a range.

The organic electroluminescent device according to (1) emits blue-violet or purple-blue light, has a long life,
An organic electroluminescent element that emits light at high luminance and consumes low power can be provided.

(10), (11), (12), (1)
The organic electroluminescent device according to (3) or (14) can provide an organic electroluminescent device that emits light with high luminance and has low power consumption with a long life.

(30), (31), (32), (3)
3) The organic compound described in (34) can provide an organic compound that emits purple-blue or blue-violet light with high luminance.

According to the inorganic phosphor described in (38),
Emits red light with an excitation wavelength between 350 and 450 nm,
An inorganic phosphor having a long life can be provided. According to the color conversion filter described in (39), 350 to
A color conversion filter that emits red light with an excitation wavelength of 450 nm and has a long life can be provided.

According to the organic electroluminescence device described in (42), an organic electroluminescence device having long life, emitting light with high luminance, and consuming low power can be provided.

Hereinafter, the present invention will be described in detail. The structure of the organic EL device will be described with reference to FIG. The organic EL device is composed of a light emitting layer 1 and electrodes composed of an anode 2 and a cathode 3. The light emitting layer 1 has a structure sandwiched between an anode 2 and a cathode 3. By applying current to the electrodes,
The organic compound contained in the light emitting layer 1 emits light. this is,
Positive and negative carriers are injected from the cathode 3 and the anode 2, and the carriers move and recombine in the organic layer, thereby forming a singlet excited state of the compound and deactivating from the singlet excited state to the ground state. It is believed that the compound emits light during the process. The organic EL element further includes a color conversion layer 4, which can convert the light of the compound contained in the light emitting layer into light having different wavelengths. FIG.
As shown in (3), full color can be realized by providing three color conversion layers having different wavelength ranges. 5
Is a substrate, and a glass substrate is usually used.

The light emitting layer will be described. In a broad sense, the light-emitting layer referred to in the present specification refers to a layer that emits light when current is applied to an electrode electrode including a cathode and an anode. Specifically, it refers to a layer containing an organic compound that emits light when a current flows. Usually, the light emitting layer has a structure in which the light emitting layer is sandwiched between a pair of electrodes. The organic EL device of the present invention
It has a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer in addition to the light emitting layer if necessary, and has a structure sandwiched between a cathode and an anode.

Specifically, (i) anode / light emitting layer / cathode (ii) anode / hole injection layer / light emitting layer / cathode (iii) anode / light emitting layer / electron injection layer / cathode (iv) anode / positive Hole injection layer / light emitting layer / electron injection layer / cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode.

Further, a cathode buffer layer (for example, lithium fluoride) may be inserted between the electron injection layer and the cathode. Further, an anode buffer layer (for example, copper phthalocyanine, etc.) may be inserted between the anode and the hole injection layer.

In the light emitting layer, a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, and the like may be provided on the light emitting layer itself. That is, (1) an injection function capable of injecting holes from an anode or a hole injection layer and injecting electrons from a cathode or an electron injection layer when an electric field is applied to the light emitting layer; It may have at least one of the functions of transporting electric charges (electrons and holes) by the force of an electric field. In this case, a hole injection layer, an electron injection layer separately from the light emitting layer Therefore, it is not necessary to provide at least one of the hole transporting layer and the electron transporting layer, so that the manufacturing cost can be reduced and the manufacturing process can be simplified. Further, the hole injection layer, the electron injection layer, the hole transport layer, the electron transport layer, and the like may contain an organic compound that emits light, so as to have a function as a light emitting layer.

In particular, the organic E of the present invention is preferably used in the electron transport layer.
When the organic compound used in the L element is contained, the function of transporting electrons is also improved, so that the light emitting layer emits light with higher luminance and power consumption can be further reduced.

As a method for forming a light emitting layer using the above materials, for example, a vapor deposition method, a spin coating method, a casting method,
Although it can be formed by thinning by a known method such as the LB method, it is particularly preferably a molecular deposition film. Here, the molecular deposition film refers to a thin film formed by depositing the compound from a gaseous state or a film formed by solidifying the compound from a molten state or a liquid state. Usually, this molecular deposited film can be distinguished from a thin film (molecule accumulation film) formed by the LB method by a difference in an aggregated structure and a higher-order structure, and a functional difference caused by the difference.

This light emitting layer is disclosed in Japanese Patent Application Laid-Open No. 57-517.
As described in No. 81, the light emitting material can be formed into a solution by dissolving the light emitting material in a solvent together with a binder such as a resin, and then thinning the solution by spin coating or the like. The thickness of the light emitting layer formed in this way is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

The band gap as used herein is the difference between the ionization potential and the electron affinity of a compound. The ionization potential and the electron affinity are determined based on the vacuum level. The ionization potential is defined as the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of a compound to a vacuum level, and the electron affinity is determined by the electron at the vacuum level being the LUMO (lowest empty molecule) of the substance. Orbit) is defined as the energy that falls to a level and stabilizes.

In the present invention, the band gap of the organic compound is determined by measuring the absorption spectrum of the vapor deposited film when the organic compound is vapor-deposited on glass at 100 nm, and measuring the wavelength Yn at the absorption edge.
m is converted to XeV. At this time, the following conversion formula was used.

Y = 10 ⁷ /(8065.541×X) The ionization potential of the organic compound is directly measured by photoelectron spectroscopy, or the electrochemically measured oxidation potential is corrected with respect to the reference electrode. Is also required. In the case of the latter method, for example, when a saturated sweet pepper electrode (SCE) is used as a reference electrode, ionization potential = oxidation potential (vs. SCE) +4.3 eV (“Molecular Semicon
ductors ", Springer-Verlag, 1985, p. 98).

In the present invention, the ionization potential Ip of the organic compound was directly measured by photoelectron spectroscopy. In particular,
Riken Keiki Co., Ltd. low energy electron spectrometer "Model AC-
1 ".

The electron affinity was determined in accordance with the band gap definition equation (band gap) = (ionization potential)-(electron affinity). "Purple Blue of CIE chromaticity coordinates" referred to in this specification
(Purple blue) or blue purplish (blue purple) "means that the light emitted from the light emitting layer of the organic EL element is measured by a spectral radiance meter CS-1000 (manufactured by Minolta),
When the measured results are applied to the CIE chromaticity coordinates shown in FIG. 2 (FIG. 4.16 (edited by The Japan Society of Color Science, published by The University of Tokyo, 1985) on page 108 of the “New Color and Color Science Handbook”), Purplish Blue (purple) Blue), Blues
h means being in the region of Purple (blue purple).

At least one of the organic EL devices of the present invention contains an organic compound having a band gap of 2.96 eV to 3.80 eV, and emits purple-blue and blue-violet light in the light-emitting layer. In particular, it is possible to make the inorganic phosphor emit light with high color conversion efficiency.

The organic compound used in the organic EL device of the present invention is particularly preferably Blue Purplis of CIE chromaticity coordinates.
It is preferable to emit light in h (blue violet), whereby the inorganic phosphor can emit light with higher color conversion efficiency.

Further, when the organic compound is an organic-inorganic compound having a hetero atom, light is emitted with higher luminance. Thereby, a higher-luminance organic EL element can be provided. Further, when the organic compound is an inter-hetero compound having at least one hetero ring, the organic compound emits light with higher luminance,
As a result, an organic EL device having higher luminance can be provided.

At least one of the organic EL devices of the present invention is particularly preferably an organic compound having a band gap of 3.20 eV to 3.60 eV from the viewpoint of color conversion efficiency.
At least one of the organic EL devices of the present invention preferably has an electron transporting layer, and the electron transporting layer preferably contains an organic compound contained in the light emitting layer of the organic EL device of the present invention. preferable. As a result, the electron transport function is improved, so that it is possible to provide an organic electroluminescence element having a longer life, emitting light with higher luminance, and consuming less power.

The organic EL device of the present invention preferably has at least one buffer layer between the light emitting layer and the cathode, whereby the life of the organic EL device can be significantly extended.

The light-emitting organic compound contained in the light-emitting layer of at least one organic EL device of the present invention preferably contains a compound represented by the following formula (I), which emits light with higher luminance. .

[0068]

Embedded image

In the general formula (I), the carbon at the center
The carbon bond can be written as follows, for example, as follows, depending on how to write the resonance structural formula, so that it can be either a single bond or a double bond.

[0070]

Embedded image

In the formula (I), Z ₁ and Z ₂ together with a carbon-carbon single bond or a carbon-carbon double bond form a 5- or 6-membered hydrocarbon ring or a heterocyclic ring. Represents a group of nonmetallic atoms necessary for For example, Z ₁ , Z ₂ and carbon
-Specific examples of a 5- or 6-membered hydrocarbon ring or a heterocyclic ring formed together with a single carbon bond or a double carbon-carbon bond include furan, thiophene, pyrrole,
Imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isoxazole, isothiazole, furazane,
Pyridine, 4-hydroxypyridine (or its tautomer), 2-hydroxypyridine (or its tautomer), pyrazine, pyrimidine, pyridazine, indolizine, quinoline, isoindole, indole, isoquinoline, phthalazine, Purine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, phenanthridine, acridine, perimidine,
Represents phenanthroline, phenazine, benzene, naphthalene, phenanthrene, anthracene, pyrene, cyclopentane, cyclohexane, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, and the like. Further, these may have a plurality of optional substituents each independently, and the plurality of substituents may be fused to each other to further form a ring. Specific examples are as follows, but are not limited thereto. * Is a site that can be a carbon-carbon bond in the general formula (I).

[0072]

Embedded image

R represents a substituent. Examples of the substituent represented by R include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a perfluoropropyl group). Group,
Perfluoro-n-butyl group, perfluoro-t-butyl group,
t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p -Chlorophenyl group and the like), alkoxy group (for example, methoxy group,
An ethoxy group, an isopropoxy group, a butoxy group and the like, an aryloxy group (for example, a phenoxy group and the like) and the like can be mentioned. These groups may be further substituted. Examples of the substituent include a halogen atom, a hydrogen atom, a trifluoromethyl group, a cyano group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and an alkylthio group. , A dialkylamino group, a dibenzylamino group, a diarylamino group and the like.

The compound represented by the general formula (I) is preferably a compound represented by the following general formulas (II) and (III) which emits light with high luminance.

[0075]

Embedded image

In the general formulas (II) and (III),
Z ₃ , Z ₄ , Z ₅ and Z ₆ represent an aromatic hydrocarbon ring or a heterocyclic ring which may have a substituent, for example, benzene, naphthalene, anthracene, azulene, phenanthrene, triphenylene, pyrene, chrysene, naphthacene , Perylene, pentacene, hexacene, coronene, trinaphthylene, furan, thiophene, pyrrole, imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isoxazole, isothiazole, furazane, pyridine 4-hydroxypyridine (or its tautomer), 2-hydroxypyridine (or its tautomer), pyrazine, pyrimidine, pyridazine, indolizine, quinoline, isoindole, indole, isoquinoline, phthalazine, purine , Nuff It represents lysine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, phenanthridine, acridine, perimidine, phenanthroline, phenazine and the like. Further, these may have a plurality of optional substituents each independently, and the plurality of substituents may be fused to each other to further form a ring.

[0077] Although R ₃ to R ₆ represents a substituent, as the substituent represented by R ₃ to R _6, alkyl group (e.g. methyl,
Ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, perfluoropropyl group, perfluoro-n-butyl group, perfluoro-t-
Butyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl) Groups, p-chlorophenyl groups, etc.), alkoxy groups (eg, methoxy groups, ethoxy groups, isopropoxy groups, butoxy groups, etc.), and aryloxy groups (eg, phenoxy groups, etc.). These groups may be further substituted. Examples of the substituent include a halogen atom, a hydrogen atom, a trifluoromethyl group, a cyano group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and an alkylthio group. , A dialkylamino group, a dibenzylamino group, a diarylamino group and the like. The general formula (I
The compounds represented by I) and (III) emit particularly high luminance, and are represented by the following general formulas (IV), (V), (VI) and (VI).
I), (VIII), (IX), (X), (XI),
The compound represented by (XII) is preferable.

[0078]

Embedded image

R _{a1 to} R _a19 each independently represent a hydrogen atom or a substituent, and the substituents represented by R _{a1 to} R _a19 include the substituents represented by R _{3 to} R ₆ Synonymous with.

The light-emitting compounds contained in the light-emitting layer of the organic EL device of the present invention include compounds represented by formulas (IV), (V), (VI), (VII) and (VII) which emit light with high luminance.
I), (IX), (X), (XI), and (XII) at least two or more of the compounds selected from the compounds represented by the formula (I) and excluding the hydrogen atom or the substituent, and non-conjugated to each other. It is preferably a compound linked by a group.

The non-conjugated linking group includes divalent, trivalent,
Value. Specific examples include a substituted or unsubstituted saturated alkylene group, an aromatic hydrocarbon ring, a heterocyclic ring, and the like. The substituted or unsubstituted saturated alkylene group may contain a heteroatom and may partially form a ring.

Specific non-conjugated linking groups are shown below. *
Represents the position where the residue binds.

[0083]

Embedded image

The formulas (IV), (V), (VI) and (V
II), (VIII), (IX), (X), (XI),
Specific examples of the compound in which each residue of at least two or more compounds selected from the compounds represented by (XII) are bonded to each other by a non-conjugated linking group include the following general formula (X
Since the compound represented by (III), (XIV) or (XV) emits light with higher luminance, it is preferable that at least one of them is contained in the light emitting layer.

[0085]

Embedded image

Z _{7 to} Z ₁₄ represent a group of nonmetallic atoms necessary for forming an aromatic hydrocarbon ring or a heterocyclic ring, and specifically, those represented by Z _{3 to} Z ₆ Synonyms are mentioned. Lx, Ly and Lz are each divalent, 3
Represents a tetravalent or tetravalent linking group. Specific examples include a substituted or unsubstituted saturated alkylene group, an aromatic hydrocarbon ring, a heterocyclic ring, and the like. The substituted or unsubstituted saturated alkylene group may contain a heteroatom and may partially form a ring.

The band gap of the organic compound represented by any of formulas (I) to (XII) is preferably from 3.20 eV to
3.60 eV, whereby blue-violet or purple-blue light can be emitted with higher luminance.

Further, the organic compounds represented by the general formulas (I) to (XII) have a high glass transition temperature (Tg), and therefore have a sufficient thermal stability as a material for an organic electroluminescence device.

Formulas (XVI), (XVII) and (XV
III), (XIX), (XX-1), (XX-2),
The organic compound represented by (XX-3) or (XX-4)
It is a compound that emits purple-blue or blue-violet light. In addition, since it is an organic compound that emits light with high luminance, it is useful as a compound that emits light in the light-emitting layer of an organic electroluminescence element, and of course, utilizes the above-mentioned properties to emit fluorescence. It can also be used as a material such as a labeling compound for pharmaceuticals used.

Further, the following general formulas (XVI) and (XVI)
I), (XVIII), (XIX), (XX-1),
Since the organic compounds represented by (XX-2), (XX-3), and (XX-4) have a high glass transition temperature (Tg), they also have sufficient thermal stability as a material for an organic electroluminescence element. is there.

Formulas (XVI), (XVII) and (XV
III), (XIX), (XX-1), (XX-2),
When the organic compound represented by (XX-3) or (XX-4) is contained in the light emitting layer of the organic EL layer, the band gap is preferably in the range of 2.96 to 3.80 eV, More preferably, the compound is in the range of 3.20 eV to 3.60 eV. As a result, blue-violet or purple-blue light can be emitted with higher luminance.

Formulas (XVI), (XVII) and (XV
III), (XIX), (XX-1), (XX-2),
The molecular weight of the compound represented by the organic compound represented by (XX-3) or (XX-4) is preferably in the range of 600 to 2,000. When the molecular weight is within this range, the light emitting layer can be easily formed by a vacuum deposition method,
Manufacturing of the L element is facilitated. Further, the thermal stability of the organic compound in the organic EL device is improved.

The specific examples of the compounds represented by formulas (I) to (XX) of the present invention are shown below, but the present invention is not limited to these.

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

In the organic EL device which is one of the present invention, the region (doping region) containing the phosphor (dopant) is not specified, and it is sufficient that the region contains the dopant. Preferably, a phosphor is contained. The thickness of the layer in the doping region is from 5 nm to 1
The thickness is preferably 00 nm. If the thickness of the doping region is too small, the effect of color conversion is small. The concentration of the fluorescent dopant used is preferably 0.001 to 10 mol%. If the concentration of the fluorescent dopant is too low, the effect of color conversion is weak, while if it is too high, concentration quenching occurs in which the excited state is deactivated without emitting light due to association of molecules.

An optional dopant is used for the organic EL device of the present invention. A preferred dopant is a fluorescent organic molecule having a high fluorescence quantum yield in a solution state, or a rare earth complex-based phosphor. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. The solution used for measuring the fluorescence quantum yield may be any solution as long as the compound is soluble, such as acetonitrile, tetrahydrofuran, cyclohexane,
Benzene, dimethylformamide, dichloromethane, toluene and the like can be considered.

The fluorescent organic molecules having a high fluorescence quantum yield include, for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squarium dyes, oxobenzanthracene dyes, fluorescein dyes, and the like.
Examples include rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, and polythiophene dyes.

As the rare earth complex phosphor, a rare earth complex phosphor described in detail later can be used.
Next, the hole injection layer and the electron injection layer will be described.

The hole injecting layer and the hole transporting layer have a function of transmitting holes injected from the anode to the light emitting layer, and the hole injecting layer and the hole transporting layer are disposed between the anode and the light emitting layer. By intervening, many holes are injected into the light emitting layer at a lower electric field, and furthermore, electrons injected from the cathode, the electron injection layer or the electron transport layer into the light emitting layer are combined with the light emitting layer and the hole injection layer or the positive hole. An electron barrier present at the interface of the hole transport layer accumulates at the interface within the light-emitting layer, resulting in an element having excellent light-emitting performance, such as improved luminous efficiency. The material of the hole injection layer and the hole transport layer (hereinafter, referred to as a hole injection material and a hole transport material) is not particularly limited as long as it has the above preferable properties. Any material can be selected from those commonly used as charge injection / transport materials for holes, hole injection layers of EL devices, and known materials used for hole transport layers.

The hole injecting material and the hole transporting material have any of hole injecting or transporting and electron barrier properties, and may be any of an organic substance and an inorganic substance.
Examples of the hole injection material and the hole transport material include a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative and a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, and oxazole. Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers, are mentioned. As the hole injecting material and the hole transporting material, those described above can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds, can be used. preferable.

Representative examples of the above aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'
N-tetraphenyl-4,4′-diaminophenyl;
N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 2,2-bis (4-di-p-tolyl Aminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′,
N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl ) Phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl;
N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- ( Di-p-tolylamino) -4'-
[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenyl Carbazole, and those having two fused aromatic rings in the molecule described in U.S. Pat. No. 5,061,569, for example, 4,4'-bis [N- (1-naphthyl) -N
-Phenylamino] biphenyl (NPD);
No. 3,068,688, in which three triphenylamine units are linked in a star-burst form.
4 ', 4''-tris [N- (3-methylphenyl) -N
-Phenylamino] triphenylamine (MTDAT
A) and the like.

Further, a polymer material in which these materials are introduced into a polymer chain, or in which these materials are used as a polymer main chain, may be used. Also, p-type-Si, p-type-S
An inorganic compound such as iC can also be used as a hole injection material and a hole transport material. The hole injection layer and the hole transport layer are formed by thinning the hole injection material and the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. Can be formed. The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm. The hole injecting layer and the hole transporting layer may have a single-layer structure composed of one or more of the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Further, the electron transporting layer used as needed may have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material may be selected from conventionally known compounds. Can be used.

The materials used for this electron transport layer (hereinafter referred to as
Examples of nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethane and Examples include anthrone derivatives and oxadiazole derivatives. Further, in the oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transporting material.

Further, a polymer material in which these materials are introduced into a polymer chain, or a polymer in which these materials are used as a main chain of a polymer may be used. Further, metal complexes of 8-quinolinol derivatives, for example, tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-
Quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-
Methyl-8-quinolinol) aluminum, bis (8-
Quinolinol) zinc (Znq) and the like, and the central metal of these metal complexes is In, Mg, Cu, Ca, Sn, Ga
Alternatively, a metal complex replaced with Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those whose terminals are substituted with an alkyl group, a sulfonic acid group, or the like can be preferably used as the electron transporting material. Further, the distyrylpyrazine derivative exemplified as a material for the light emitting layer can also be used as an electron transporting material, and a hole injection layer,
Similarly to the hole transport layer, an inorganic semiconductor such as n-type Si or n-type SiC can be used as the electron transport material.

This electron transport layer can be formed by forming the above compound by a known thinning method such as a vacuum evaporation method, a spin coating method, a casting method, and an LB method. The thickness of the electron transport layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. The electron transport layer may have a single-layer structure composed of one or more of these electron transport materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

The substrate preferably used for the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is not particularly limited as long as it is transparent.
Examples of the substrate preferably used for the electroluminescence device of the present invention include glass, quartz, and a light-transmitting plastic film.

The light-transmitting plastic films include:
For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose A film made of acetate propionate (CAP) or the like can be used.

Next, a preferred example of manufacturing the organic EL device will be described. As an example, a method of manufacturing an EL device including the above-described anode / hole injection layer / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode will be described. First, a desired electrode is formed on a suitable substrate. A thin film made of a substance, for example, a substance for an anode is formed by a method such as evaporation or sputtering so as to have a thickness of 1 μm or less, preferably 10 to 200 nm, to produce an anode. Next, a thin film composed of a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer / electron injection layer, which are element materials, is formed thereon.

Further, a buffer layer (electrode interface layer) may be present between the anode and the light emitting layer or the hole injection layer and between the cathode and the light emitting layer or the electron injection layer. The buffer layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminous efficiency. “The organic EL device and the forefront of its industrialization (published by NTT Corporation on November 30, 1998) )), Vol. 2, Chapter 2, “Electrode Materials” (pages 123 to 166), which includes an anode buffer layer and a cathode buffer layer.

The anode buffer layer is described in JP-A-9-45479,
Nos. 9-260062 and 8-288069, the details of which are also described.As specific examples, phthalocyanine buffer layers represented by copper phthalocyanine, oxide buffer layers represented by vanadium oxide, amorphous carbon buffers And a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

The cathode buffer layer is described in JP-A-6-325871,
Nos. 9-17574, 10-74586 and the like are also described in detail, specifically, metal buffer layers represented by strontium and aluminum, etc., alkali metal compound buffer layers represented by lithium fluoride And an alkaline earth metal compound buffer layer represented by magnesium fluoride, an oxide buffer layer represented by aluminum oxide, and the like.

It is desirable that the buffer layer is a very thin film.
A range of 0 nm is preferred. In addition to the above-mentioned basic constituent layers, layers having other functions may be laminated as necessary. For example, JP-A-11-204258, JP-A-11-204359, and "Organic EL devices and the forefront of industrialization ( (November 30, 1998, published by NTT Co., Ltd.), page 237, etc., etc., and may have a functional layer such as a hole blocking (hole block) layer.

The buffer layer may function as a light emitting layer when at least one of the compounds of the present invention is present in at least one of the cathode buffer layer and the anode buffer layer.

Next, the electrodes of the organic EL device will be described. The electrodes of the organic EL element are composed of a cathode and an anode. As the anode in the organic EL element, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au, CuI, indium tin oxide (ITO), and Sn.
Conductive transparent materials such as O ₂ and ZnO are mentioned.

The above-mentioned anode may be formed by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering and forming a pattern of a desired shape by a photolithography method. (About 100 μm or more), a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. When light is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance of the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually 10 nm to 1 μm.
m, preferably in the range of 10 nm to 200 nm.

On the other hand, as the cathode, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are used as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum /
Examples include an aluminum oxide (Al ₂ O ₃ ) mixture, indium, a lithium / aluminum mixture, and a rare earth metal. Among them, a mixture of an electron-injecting metal and a second metal, which is a metal having a large work function and a stable work function, such as a magnesium / silver mixture, magnesium, / Aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture, and the like are preferable.

Further, the cathode used in the organic EL device of the present invention is preferably an aluminum alloy, particularly preferably having an aluminum content of 90% by mass or more and less than 100% by mass, and most preferably 95% by mass or more and 100% by mass. Is less than. Thereby, the light emission lifetime and the highest attainable luminance of the organic EL element can be further improved.

The above-mentioned cathode can be manufactured by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually 10
It is selected in the range of nm to 1 μm, preferably 50 to 200 nm. In order to transmit light, if either one of the anode and the cathode of the organic EL element is transparent or translucent, the luminous efficiency is improved, which is convenient.

The method for thinning the organic thin film layer is as follows.
As described above, there are a spin coating method, a casting method, a vapor deposition method, and the like, but a vacuum vapor deposition method or a spin coating method is particularly preferable in that a uniform film is easily obtained and a pinhole is not easily generated. Further, a different film forming method may be applied to each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, and the like. ^-6 to 10 ^-2 P
a, deposition rate 0.01 to 50 nm / sec, substrate temperature -50
It is preferable to appropriately select a temperature within a range of from about 300 ° C. to a thickness of from 5 nm to 5 μm.

After forming these layers, a thin film made of a material for a cathode is formed thereon with a thickness of 1 μm or less, preferably 50 to 200 nm.
A desired EL element can be obtained by forming a film having a thickness in the range of m by, for example, a method such as vapor deposition or sputtering and providing a cathode. In the production of this organic EL element, it is preferable to consistently produce from the hole injection layer to the cathode by a single evacuation, but it is also possible to take out and apply a different film forming method in the middle. It is necessary to consider that the work is performed in a dry inert gas atmosphere.

It is also possible to reverse the order of the fabrication to produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the EL element thus obtained, light emission can be observed by applying a voltage of about 5 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Also, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. further,
When an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The waveform of the applied alternating current may be arbitrary.

Next, the color conversion layer will be described. The color conversion layer referred to in this specification refers to a layer having a function of converting light of a certain wavelength into light of a different wavelength in a broad sense.
Specifically, it refers to a layer containing a substance that absorbs light and emits light of different wavelengths.

The organic EL device of the present invention preferably has a color conversion layer containing a phosphor. Thereby, the organic EL element is not limited to the color of light emitted from the light emitting layer,
Other colors converted by the color conversion layer can also be displayed.

The phosphor contained in the color conversion layer used in the present invention particularly preferably contains an inorganic phosphor. Thereby, the light emitted from the light emitting layer of the organic EL element is converted with high color conversion efficiency, so that the power consumption of the organic EL element can be suppressed.

As the color conversion layer used in the present invention, 400 to 500
a color conversion layer containing an inorganic phosphor that emits light having a maximum emission wavelength in the range of nm, and having a maximum emission wavelength in the range of 501 to 600 nm when excited by the emission wavelength of the organic compound in the emission layer. A color conversion layer containing an inorganic phosphor that emits light.
Excited at the emission wavelength of the organic compound in the emission layer
It is preferable to have at least a color conversion layer containing an inorganic phosphor that emits light having a maximum emission wavelength in the range of 00 nm. As a result, the organic EL element can be made full color.

Further, as long as efficient full-color printing can be achieved, four or more color conversion layers may be provided. The composition of the inorganic phosphor is not particularly limited, but is Y ₂ O ₂ S, Zn ₂ SiO ₄ , Ca ₅ (PO ₄ ) ₃ Cl which is a crystal base material.
Such as metal oxides and ZnS, SrS, CaS
Such as Ce, Pr, Nd, Pm, S
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb
And rare earth metal ions such as Ag, Al, Mn, In, C
A combination of metal ions such as u and Sb as an activator or co-activator is preferred.

The crystal matrix will be described in more detail. As the crystal matrix, a metal oxide is preferable. For example, (X) ₃ Al
₁₆ O ₂₇ , (X) ₄ Al ₁₄ O ₂₅ , (X) ₃ Al ₂ Si ₂ O ₁₀ ,
(X) ₄ Si ₂ O ₈ , (X) ₂ Si ₂ O ₆ , (X) ₂ P ₂ O ₇ ,
(X) ₂ P ₂ O ₅ , (X) ₅ (PO ₄ ) ₃ Cl, (X) ₂ Si ₃
O ₈ -2 (X) Cl ₂ [where X represents an alkaline earth metal. The alkaline earth metal represented by X may be a single component or a mixture of two or more types, and the mixing ratio may be arbitrary. ], Aluminum oxide, silicon oxide, phosphoric acid, halophosphoric acid and the like substituted with an alkaline earth metal as described above.

Other preferable crystal bases include oxides and sulfides of zinc, oxides of rare earth metals such as yttrium, gadolinium and lanthanum, and a part of oxygen of the oxides converted to sulfur atoms (sulfides). And sulfides of rare-earth metals, and oxides and sulfides thereof mixed with an arbitrary metal element.

Preferred examples of the crystal base are listed below.
Mg_FourGeO_5.5F, Mg_FourGeO₆, ZnS, Y_TwoO_TwoS,
Y_ThreeAl_FiveO₁₂, Y_TwoSiO_Ten, Zn_TwoSiO_Four, Y_TwoO_Three,
BaMgAl_TenO₁₇, BaAl₁₂O₁₉, (Ba, Sr,
Mg) O ・ aAl_TwoO_Three, (Y, Gd) BO_Three, (Zn,
Cd) S, SrGa_TwoS_Four, SrS, GaS, SnO_Two,
Ca_Ten(PO_Four)₆(F, Cl)_Two, (Ba, Sr) (M
g, Mn) Al_TenO₁₇, (Sr, Ca, Ba, Mg)_Ten
(PO_Four)₆Cl_Two, (La, Ce) PO_Four, CeMgAl
₁₁O₁₉, GdMgB_FiveO_Ten, Sr_TwoP _TwoO₇, Sr_FourAl₁₄
O_{twenty five}, Y_TwoSO_Four, Gd_TwoO_TwoS, Gd_TwoO_Three, YVO_Four, Y
(P, V) O_FourAnd so on.

The above-mentioned crystal matrix and activator or co-activator may be partially substituted with homologous elements.
There is no particular limitation on the elemental composition, as long as it absorbs light in the ultraviolet region or light in the purple region and emits visible light.

In the present invention, La, Eu, Tb, and C are preferable as activators and coactivators of the inorganic phosphor.
e, ions of a lanthanoid element typified by Yb, Pr, and the like, and ions of metals such as Ag, Mn, Cu, In, and Al.
00 mol% is preferable, and 0.01 to 50 mol% is more preferable.

The activator and co-activator constitute the crystal matrix.
Replace some of the on with ions like lanthanoids above
By doing so, it is doped into the crystal. Phosphor crystal
Strictly speaking, the actual composition is expressed by the following composition formula.
However, the amount of activator may affect the intrinsic fluorescence properties.
In most cases, it will not affect the following, unless otherwise specified
The values of x and y below are not described. For example, S
r _4-xAl₁₄O_{twenty five}: Eu²⁺ _xIs Sr in the present invention._Four
Al₁₄O_{twenty five}: Eu²⁺Notation.

The inorganic phosphor used in the color conversion layer of the organic EL device of the present invention preferably contains an inorganic phosphor represented by the following general formula (A). General formula (A) M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2Z is satisfied. (n may be 0.) By using the inorganic phosphor represented by the general formula (A), a longer life and higher color conversion efficiency can be obtained, so that a longer life and lower power consumption organic EL element is provided. can do.

The inorganic phosphor represented by the general formula (A) is 6
The phosphor preferably has a maximum emission wavelength in the range of 01 to 700 nm, and in the phosphor represented by the general formula (A), M is preferably magnesium. Thereby, an organic EL element having high red purity can be provided.

The inorganic phosphor used for the color conversion layer preferably contains an inorganic phosphor represented by the following general formula (B). Formula _{(B) N u E uy (} W 1-t MoO 4) w ( however, M is an alkaline earth metal, 2W = u + 3
v, and t is an integer of 0 or 1. By using the inorganic phosphor represented by the general formula (B), a longer life and higher color conversion efficiency can be obtained, so that an organic EL element having a longer life and lower power consumption can be provided.

The inorganic phosphor represented by the general formula (B) is 6
The phosphor preferably has a maximum emission wavelength in the range of 01 to 700 nm, and in the phosphor represented by the general formula (B), N is preferably potassium. Thereby, an organic EL element having high red purity can be provided.

The following are representative inorganic phosphors (crystal base and
Composition formula of inorganic phosphor composed of activator)
However, the present invention is not limited to these.
(Ba _z Mg_1-z)_3-xyAl₁₆O₂₇: Eu²⁺ _x, M
n²⁺ _y, Sr_4-xAl₁₄O_{twenty five}: Eu²⁺ _x, (Sr_1-z Ba
_z)_1-xAl_TwoSi_TwoO₈: Eu²⁺ _x, Ba_2-xSiO_Four: Eu
²⁺ _x, Sr_2-xSiO_Four: Eu²⁺ _x, Mg_2-xSiO_Four: Eu
²⁺ _x, (BaSr)_1-xSiO_Four: Eu²⁺ _x, Y_2-xySi
O_Five: Ce³⁺ _x, Tb³⁺ _y, Sr_2-xP_TwoO_Five: Eu²⁺ _x,
Sr_2-xP_TwoO₇: Eu²⁺ _x, (Ba_yCa_zMg_1-yz)_5-x
(PO_Four)_ThreeCl: Eu_{2+ x}, Sr_2-xSi_ThreeO₈-2SrC
l_Two: Eu²⁺ _x [X, y and z are each less than or equal to 1
It represents the number of the meaning. The following shows the inorganic phosphor preferably used in the present invention.
However, the present invention is not limited to these compounds.
No. [Blue-emitting inorganic phosphor] (BL-1) Sr_TwoP_TwoO₇: Sn⁴⁺ (BL-2) Sr_FourAl₁₄O_Two5: Eu²⁺ (BL-3) BaMgAl_TenO₁₇: Eu²⁺ (BL-4) SrGa_TwoS_Four: Ce³⁺ (BL-5) CaGa_TwoS_Four: Ce³⁺ (BL-6) (Ba, Sr) (Mg, Mn) Al_TenO₁₇: Eu²⁺ (BL-7) (Sr, Ca, Ba, Mg)_Ten(PO_Four)₆Cl_Two: Eu²⁺ (BL-8) BaAl_TwoSiO₈: Eu²⁺ (BL-9) Sr_TwoP_TwoO₇: Eu²⁺ (BL-10) Sr_Five(PO_Four)_ThreeCl: Eu²⁺ (BL-11) (Sr, Ca, Ba)_Five(PO_Four)_ThreeCl: Eu²⁺ (BL-12) BaMg2Al16O27: Eu2 + (BL-13) (Ba, Ca)_Five(PO_Four)_ThreeCl: Eu²⁺ (BL-14) Ba_ThreeMgSi_TwoO₈: Eu²⁺ (BL-15) Sr_ThreeMgSi_TwoO₈: Eu²⁺ [Green-emitting inorganic phosphor] (GL-1) (BaMg) Al₁₆O₂₇: Eu²⁺, Mn²⁺ (GL-2) Sr_FourAl₁₄O_{twenty five}: Eu²⁺ (GL-3) (SrBa) Al_TwoSi_TwoO₈: Eu²⁺ (GL-4) (BaMg)_TwoSiO_Four: Eu²⁺ (GL-5) Y_TwoSiO_Five: Ce³⁺, Tb³⁺ (GL-6) Sr_TwoP_TwoO₇-Sr_TwoB_TwoO_Five: Eu²⁺ (GL-7) (BaCaMg)_Five(PO_Four)_ThreeCl: Eu²⁺ (GL-8) Sr_TwoSi_ThreeO₈-2SrCl_Two: Eu²⁺ (GL-9) Zr_TwoSiO_Four, MgAl₁₁O₁₉: Ce³⁺, Tb³⁺ (GL-10) Ba_TwoSiO_Four: Eu²⁺ (GL-11) Sr_TwoSiO_Four: Eu²⁺ (GL-12) (BaSr) SiO_Four: Eu²⁺ [Red-Emitting Inorganic Phosphor] (RL-1) Y_TwoO_TwoS: Eu³⁺ (RL-2) YAlO_Three: Eu³⁺ (RL-3) Ca_TwoY_Two(SiO_Four)₆: Eu³⁺ (RL-4) LiY₉(SiO_Four)₆O_Two: Eu³⁺ (RL-5) YVO_Four: Eu³⁺ (RL-6) CaS: Eu³⁺ (RL-7) Gd_TwoO_Three: Eu³⁺ (RL-8) Gd_TwoO_TwoS: Eu³⁺ (RL-9) Y (P, V) O_Four: Eu³⁺ (RL-10) Mg_FourGeO_5.5F: Mn⁴⁺ (RL-11) Mg_FourGeO₆: Mn⁴⁺ (RL-12) K_FiveEu_2.5(WO_Four)_6.25 (RL-13) Na_FiveEu_2.5(WO_Four)_6.25 (RL-14) K_FiveEu_2.5(MoO_Four)_6.25 (RL-15) Na_FiveEu_2.5(MoO_Four)_6.25 The inorganic phosphor is subjected to a surface modification treatment as necessary.
May be used, such as a silane coupling agent or the like.
Fine particles on the order of submicron, due to chemical treatment
By physical treatment by the addition of
And the like in combination.

As the silane coupling agent, those described in “NUC Silicone Silane Coupling Agent” catalog issued by Nippon Unicar Co., Ltd. (August 2, 1997) can be used as they are. , Β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyl tree n-propyloxysilane, γ-methacryloyloxy-n-propyl-n-propyloxysilane , Di (γ-acryloyloxy-n-propyl) di-n-propyloxysilane, acryloyloxydimethoxyethylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldime Kishishiran, .gamma.-aminopropyltriethoxysilane, N- phenyl-.gamma.-aminopropyltrimethoxysilane, etc. .gamma.-mercaptopropyl trimethoxysilane.

The fine particles are preferably inorganic fine particles, for example, fine particles of silica, titania, zirconia, zinc oxide and the like. From the viewpoint of emission intensity, the inorganic phosphor preferably does not undergo a mechanical crushing step during production, that is, is synthesized by a build-up method, and is particularly preferably manufactured by a Sol-Gel method or the like. Further, from the viewpoint of composition, an inorganic oxide as a base is preferable. The color conversion efficiency can be further improved.

The method of production by the Sol-Gel method is described in detail in, for example, "Application of the Sol-gel Method" by Saio Sakuhana (published by Agne Shofusha in 1997). Starting from the sol-gelation of the solution, it means a method of synthesizing the material at a lower temperature than the melting method, and the “Sol-Gel method” in the present invention refers to the liquid phase in at least one step of phosphor production. This method refers to performing a reaction by a method, and can be distinguished from a synthesis method performed by a melting reaction applied to ordinary synthesis of an inorganic phosphor. In the Sol-Gel method of the present invention, generally, an element (metal) used for a matrix, an activator, or a coactivator is, for example, tetramethoxysilane (Si (OCH
₃ ) Metal alkoxide or metal complex such as ₄ ) or europium-2,4-pentanedionate (Eu ³⁺ (CH ₃ COCH = C (O-) CH ₃ ) ₃ ), or a metal simple substance in an organic solvent solution thereof. in addition double alkoxide (Mg making e.g. Al (OBu) ₃ 2-butanol solution was added magnesium metal [Al (OBu) _{3] 2,} etc.) to make it, metal halides, metal salts of organic acids, necessary as elemental metals It means a production method in which the components are mixed in quantity and thermally or chemically polycondensed in a liquid phase state, and may be subjected to calcination or reduction treatment, if necessary.

The “metal” of the metal alkoxide, metal halide, metal salt or metal used in the present invention is generally defined as “metals (Me
tals) ”as well as“ Transition metal (Transition)
Metals), all elements of "lanthanoids", all elements of "actinoids" and defined as including boron, silicon (silicon) defined as "Non Metals" . In particular, in the case of manufacturing by the Sol-Gel method, a phosphor precursor solution or a solution containing primary particles is patterned on a transparent substrate by a printing method, an inkjet method, or the like, and then subjected to a crystallization treatment such as a baking or reduction treatment or a high brightness. Processing may be performed.

The inorganic phosphor is preferably a rare earth complex phosphor. As a result, the color conversion efficiency is improved, and the power consumption of the organic EL element can be further reduced.

As the rare earth complex phosphor, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
Examples include those having b, Dy, Ho, Er, Tm, and Yb. The organic ligand forming the complex may be either an aromatic ligand or a non-aromatic ligand, and is preferably represented by the following general formula (C): The compound represented by is preferred.

[0153] Formula _{(C) Xa- (L x)} - (L y) n - in (L _z) -Ya [wherein, L _x, L _y, two or more bonding hands L _z each independently And n represents 0 or 1, and X
a represents a substituent having an atom capable of coordinating adjacent to L _x , and Ya represents a substituent having an atom capable of coordinating adjacent to L _Z. Further, any part of Xa and L _X may be fused to each other to form a ring, and any part of Ya and L _X
z and may form a ring fused to each other, L _x and L _z and may form a ring condensed with each other, is more aromatic hydrocarbon rings or aromatic heterocyclic rings in the molecule at least There is one. _{However, Xa- (L x) - (} L y) n - (L z)
-Ya is a β-diketone derivative, β-ketoester derivative, β-ketoamide derivative or the above ketone, in which the oxygen atom is a sulfur atom or —N (R ₂₀₁ ) —, (R ₂₀₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group), an oxygen atom of crown ether, azacrown ether, thiacrown ether or crown ether is replaced by an arbitrary number of sulfur atoms or -N ( _R201 )-. When a crown ether is represented, an aromatic hydrocarbon ring or an aromatic hetero ring may not be present. In the general formula (C), the coordinable atoms represented by Xa and Ya are specifically an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom.
It is preferably a nitrogen atom or a sulfur atom.

In formula (C), the atom having two or more bonds represented by L _x , L _y , and L _z is not particularly limited, but is typically a carbon atom, an oxygen atom, Examples include a nitrogen atom, a silicon atom, a titanium atom and the like, and a preferable one is a carbon atom.

Hereinafter, specific examples of the rare earth complex-based phosphor represented by the general formula (C) will be shown, but the present invention is not limited thereto.

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

Next, the color conversion filter according to the present invention will be described. The color conversion filter referred to in the present invention is:
A wavelength conversion element used to convert the color (emission color) of a light source to a desired color. Basically, a wavelength conversion element that can convert a wavelength to a wavelength longer than the maximum maximum wavelength of the light source by 10 nm or more. Yes, as a specific application,
No. 152897, No. 9-245511, No. 11-29
No. 7777, etc. (a color conversion filter that converts blue light into green and red and arranges them in stripes to emit blue, green, and red light), lighting, White light emission filter for backlight of liquid crystal display (40
A color conversion filter that emits a wide range of light in the visible range from 0 to 700 nm), a filter for partial emission of neon signs and instrumentation of automobiles (a color conversion filter for displaying necessary colors where necessary), and the like. Typical examples are given below. The color conversion filter is useful when used as a color conversion layer of an organic EL device.

As the general formula (A) contained in the color conversion filter of the present invention, it is preferable to use the specific examples of the general formula (A) described above, whereby the color can be efficiently converted.

[0165]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Synthesis of Organic Compound Example 1-1 Synthesis of Organic Compound (XVI-1) 5.0 g of tris (2,5-dimethyl, 4-bromo) amine was dissolved in 300 cc of dry tetrahydrofuran under a nitrogen atmosphere. Then, the mixture was cooled to -78 degrees with dry ice / acetone. To this reaction solution, n-butyllithium n-hexane solution 30c
c was added dropwise over 30 minutes. After stirring for 1 hour, 5 g of dry ice was quickly added. Thereafter, after stirring for a while, tetrahydrofuran was distilled off under reduced pressure, ethyl acetate and water were added, and the organic layer was extracted. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure and recrystallized from acetic acid and methanol to obtain 3.0 g of tris (2,5-dimethyl, 4-carboxy) amine (yield 74%).

Next, 3.0 g of tris (2,5-dimethyl, 4-carboxy) amine and 2.7 g of 2,3-diaminofuran were dissolved in 20 g of polyphosphoric acid under a nitrogen atmosphere. The reaction solution was heated and stirred at 200 degrees for 4 hours. Thereafter, the reaction solution was drained, adjusted to pH = 8.0 with sodium carbonate, and filtered. The obtained crystals were washed with dimethylformamide and filtered to obtain 2.7 g of Tris (2,2).
5-Dimethyl, 4-benzimidazolyl) amine was obtained (yield 62%).

1.0 g of tris (2,5-dimethyl, 4-benzimidazolyl) amine was heated to 100 ° C. together with 1.0 g of potassium carbonate and 0.8 g of n-bromobutane in 20 cc of N—N-dimethylacetamide for 2 hours. Reacted. After that, water was drained, and ethyl acetate and water were added to the obtained crystals to extract an organic layer. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Purification by column chromatography with a ratio of ethyl acetate to toluene of 7: 3 yielded the desired compound (XVI-1)
0.7 g was obtained.

When the fluorescence spectrum of the target organic compound was measured in acetonitrile, the fluorescence wavelength was 417 nm.
(Excitation wavelength: 355 nm), the fluorescence quantum yield was 0.24, and it was found to emit blue-violet light with high luminance.

The ionization potential was 5.70 eV, the band gap was 3.12 eV, and the electron affinity was 2.58 eV. Example 1-2 Synthesis of Organic Compound XVII-1 5.0 g of tris (2,5-dimethyl, 4-bromo) amine was dissolved in 300 cc of dry tetrahydrofuran under a nitrogen atmosphere, and cooled to −78 ° C. with dry ice / acetone. did. To this reaction solution, n-butyllithium n-hexane solution 30c
c was added dropwise over 30 minutes. After stirring for 1 hour, 5 g of dry ice was quickly added. Thereafter, after stirring for a while, tetrahydrofuran was distilled off under reduced pressure, ethyl acetate and water were added, and the organic layer was extracted. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure and recrystallized from acetic acid and methanol to obtain 3.0 g of tris (2,5-dimethyl, 4-carboxy) amine (yield 74%).

Next, 3.0 g of tris (2,5-dimethyl, 4-carboxy) amine and 3.9 g of orthophenylenediamine were added to
It was dissolved in 20 g of polyphosphoric acid under a nitrogen atmosphere. Reaction solution 200
And stirred for 4 hours. Then, drain the reaction solution,
The pH was adjusted to 8.0 with sodium carbonate, and the mixture was filtered. The obtained crystals were washed with dimethylformamide and filtered to obtain 2.7 g of tris (2,5-dimethyl, 4-benzimidazolyl) amine (yield 62%).

1.0 g of tris (2,5-dimethyl, 4-benzimidazolyl) amine was heated to 100 ° C. together with 1.0 g of potassium carbonate and 0.8 g of n-bromobutane in 20 cc of NN-dimethylacetamide for 2 hours. Reacted. After that, water was drained, and ethyl acetate and water were added to the obtained crystals to extract an organic layer. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Purification by column chromatography with a ratio of ethyl acetate to toluene of 7: 3 yielded the desired organic compound (XVI-
1.0 g of 1) was obtained. (Yield 80%) It was confirmed by NMR and mass spectrometry that the compound was the target organic compound (XVII-1).

When the fluorescence spectrum of the target organic compound was measured in acetonitrile, the fluorescence wavelength was 413 nm.
(Excitation wavelength: 348 nm), the fluorescence quantum yield was 0.27, and it was found to emit blue-violet light with high luminance.

The ionization potential was 5.72 eV, the band gap was 3.27 eV, and the electron affinity was 2.45 eV. Example 1-3 Synthesis of Organic Compound (XVIII-1) In Example 1-1, orthophenylenediamine was used.
0.8 g of compound (XVIII-1) was prepared in the same manner as in Example 10 except that 3.9 g was replaced with 4.5 g of 3,4-diaminopyridine.
Synthesized. When the fluorescence spectrum of the target compound was measured in acetonitrile, it was found that the fluorescence wavelength was 406 nm (excitation wavelength was 349 nm), the fluorescence quantum yield was 0.18, and the light was emitted with high luminance in blue-violet.

The ionization potential was 5.78 eV, the band gap was 3.24 eV, and the electron affinity was 2.54 eV. Example 1-4 Synthesis of Organic Compound (XIX-1) The synthesis route is shown below.

[0176]

Embedded image

5.0 g of the compound (12-1) was dissolved in 200 cc of acetonitrile, 12.0 g of the compound (12-2) was added, and the mixture was stirred at room temperature for 8 hours. Thereafter, the mixture was cooled on ice, filtered and dried to obtain 7.9 g of a white compound (12-3).

7.0 g of the compound (12-3) was dissolved in 200 cc of methanol, 2.8 g of hydroxylamine hydrochloride and 3.3 g of sodium acetate dissolved in 50 cc of water were added, and the mixture was heated under reflux for 1 hour. The methanol is distilled off under reduced pressure and filtered.
6.2 g of white crystals (amide oxime form) were obtained.

4.0 g of the amide oxime was added to 300 cc of toluene.
, 1.5 g of pyridine was added, and the mixture was cooled with ice.
To this reaction solution, 3.4 g of tosylic acid chloride was added dropwise over 10 minutes. Then, after heating and refluxing for 5 hours, the solution was left to cool overnight, whereby crystals were deposited. The crystals were filtered and recrystallized from methanol to obtain 2.8 g of compound (12-4). 2.5 g of compound (12-4) was added to tetrahydrofuran 20
Dissolve in 0cc, potassium carbonate 2.0g, n-bromobutane 2.
The mixture was heated under reflux with 1 g for 2 hours. Thereafter, tetrahydrofuran was distilled off under reduced pressure, ethyl acetate and water were added, and the organic layer was extracted. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Recrystallization from acetonitrile gave 2.7 g of organic compound (XIX-1).

When the fluorescence spectrum of the target compound was measured in acetonitrile, it was found that the fluorescence wavelength was 412 nm (excitation wavelength was 354 nm), and the fluorescence quantum yield was 0.31, and the light was emitted in blue-violet with high luminance.

The ionization potential was 5.63 eV, the band gap was 3.15 eV, and the electron affinity was 2.48 eV. Example 1-5 Synthesis of Organic Compound (XX-1) The synthesis route is shown below.

[0182]

Embedded image

8.0 g of the compound (14-1) was dissolved in 150 cc of acetic acid, and 4.7 g of phenylhydrazine was added dropwise at 0 °. After the completion of the dropwise addition, the mixture was stirred at 100 degrees for 1 hour. Then, ethyl acetate and water were added, and the organic layer was extracted. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Next, the residue was purified by column chromatography in a ratio of ethyl acetate to hexane of 1:13 to obtain 4.2 g of a compound (14-2). (Yield 38
%) Next, 3.0 g of compound (14-2) and 2.
7 g was dissolved in 100 cc of tetrahydrofuran, and 3.0 g of triethylamine was added. The reaction solution was heated and stirred for 24 hours. Thereafter, tetrahydrofuran was distilled off under reduced pressure, ethyl acetate and water were added, and the organic layer was extracted. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Next, the residue was purified by column chromatography in a ratio of ethyl acetate to hexane of 1: 9 to obtain 2.1 g of an organic compound (XX-1). When the fluorescence spectrum of the target organic compound was measured in acetonitrile, the fluorescence wavelength was 403 nm (the excitation wavelength was 3%).
34 nm), and the fluorescence quantum yield was 0.65, indicating that the light emitted was blue-violet with high luminance.

The ionization potential was 5.53 eV, the band gap was 3.30 eV, and the electron affinity was 2.23 eV. Example 2 Synthesis of Inorganic Phosphor Example 2-1-1 Red Light Emitting Fine Particle Inorganic Phosphor (RL-
11) Synthesis of Mg ₄ GeO ₆ : Mn ^{4+ To} ammonia water containing 0.016 mol of ammonia, 150 ml of ethanol and 150 ml of water were added to prepare an alkaline solution.

Further, tetraethoxygermanium10.
0 g (0.04 mol) and manganese (IV) sulfate 0.03
A solution obtained by dissolving 0 g (0.2 mmol) in 150 ml of ethanol was added to the above-mentioned alkaline solution at room temperature with stirring at a dropping rate of about 1 ml / min to prepare a sol solution. The obtained sol is about 15 times (about 30 m
1), and 295 ml of a 0.3 mol / l aqueous solution of magnesium nitrate was added thereto to cause gelation.

The obtained wet gel was aged at 60 ° C. overnight in a closed container. Thereafter, the mixture was stirred and dispersed in ethanol (about 300 ml), separated by suction filtration using filter paper (Advantec 5A), and dried at room temperature. The dried gel is subjected to a heat treatment at 1000 ° C. for 2 hours in a 5% H 2 —N 2 atmosphere, and the inorganic phosphor RL—which shines red under sunlight.
11: Got the ^{_{(Mg 4 GeO 6 Mn 4+)}} 2.7g.

Conventionally, a solid phase method or a melting method has been adopted for the production of an inorganic phosphor. However, in these methods, the distribution of each metal oxide is not uniform, and the reaction is not uniform. Therefore, the composition of the obtained inorganic phosphor is not uniform, and it is difficult to stabilize the characteristics. . Further, since there is a problem that impurities are easily mixed and characteristics are deteriorated, sol-
A method for producing a high-purity inorganic phosphor having a uniform composition by the gel method was employed.

The composition of RL-11 was analyzed by XRD spectrum. As a result, it was found that the main component was Mg ₄ GeO ₆ and the minor components contained were Mg ₃ GeO ₅ and Mg ₅ GeO ₇ . RL-11 has an average particle size of 0.85 μm and an emission maximum wavelength of 660 nm (excitation light 420 nm) measured in acetonitrile.
It was found that the phosphor emits red light. RL-
Since 11 is an inorganic phosphor, it has a longer life than an organic phosphor. It is a substance that can efficiently convert light of 350 to 450 nm into red light and has a long life, so that it is useful as an inorganic phosphor added to a conversion layer of an organic EL device.

Example 2-1-2 Inorganic phosphor (RL-
12) Synthesis of K ₅ Eu _2.5 (WO ₄ ) _6.25 Aqueous ammonia containing 0.016 mol of ammonia was added to 150 ml of ethanol and 150 ml of water to prepare an alkaline solution.

Further, 23.2 g (0.04 mol) of a tungsten (IV) acetylacetenate complex and 9.7 of a europium (III) acetylacetenate complex dihydrate were used.
g (0.02 mol) in 150 ml of ethanol was dropped into the alkaline solution at room temperature at a rate of about 1 m.
The solution was added while stirring at 1 / min to prepare a sol solution.
The obtained sol was concentrated about 15 times (30 ml) by an evaporator, and 295 ml of a 0.3 mol / l aqueous solution of potassium nitrate was added thereto to gel.

The obtained wet gel was aged at 60 ° C. overnight in a closed container. Thereafter, the mixture was stirred and dispersed in ethanol (about 300 ml), separated by suction filtration using filter paper (Advantec 5A), and dried at room temperature. The dried gel is subjected to an aging treatment in a 5% H2-N2 atmosphere at 1000 ° C. for 2 hours, and the inorganic phosphor R which glows red under the sunlight
_{L-12 (K 5 Eu 2.5} (WO 4) 6.25) was obtained 3.2 g.

RL-12 was found to be a phosphor which emits red light having an average particle size of 1.15 μm and an emission maximum wavelength of 615 nm (excitation light: 394 nm). Example 2-2 Inorganic phosphor (GL-10) Ba ₂ S
Synthesis of iO ₄ : Eu ²⁺ 150 ml of ethanol and 150 ml of water were added to aqueous ammonia containing 0.016 mol of ammonia to prepare an alkaline solution.

Further, 8.33 g of tetraethoxysilane
(0.04 mol) and a solution obtained by dissolving 0.097 g (0.2 mmol) of europium (III) acetylacetonate complex dihydrate in 150 ml of ethanol were dropped into the alkaline solution at room temperature at a rate of about 1 ml. The mixture was added while stirring at a rate of / min to prepare a sol solution. The obtained sol was concentrated about 15 times (about 30 ml) by an evaporator, and 295 ml of a 0.3 mol / l barium nitrate aqueous solution was added thereto.
It was added and gelled.

The obtained wet gel was aged at 60 ° C. in a closed container overnight. Thereafter, the mixture was stirred and dispersed in ethanol (about 300 ml), separated by suction filtration using filter paper (Advantec 5A), and dried at room temperature. The dried gel is subjected to a heat treatment in a 5% H ₂ —N ₂ atmosphere at 1000 ° C. for 2 hours, and the inorganic phosphor GL which glows light green under sunlight is obtained.
2.7 g of -10 (Ba ₂ SiO ₄ : Eu ²⁺ 0.005) was obtained.

The composition of GL-10 was analyzed by XRD spectrum. As a result, it was found that the main component was Ba ₂ SiO ₄ , and the minor components contained were BaSiO ₃ and Ba ₃ SiO ₅ .

GL-10 was found to be a phosphor which emits green light having an average particle size of 1.05 μm and a maximum emission wavelength of 510 nm (excitation light: 405 nm). Example 2-3
Inorganic phosphor (BL-3) BaMgAl ₁₀ O ₁₇ : Eu
Synthesis of ^{2+ In} Example 2-2, except that tetraethoxysilane was changed to 8.2 g of isopropoxyl aluminum and the aqueous barium nitrate solution was changed to 300 ml of a 1: 1 mixed aqueous solution of barium nitrate and magnesium nitrate, In the same manner, a blue light-emitting inorganic phosphor (BL-3) (average particle size 0.90 μm, maximum light emission wavelength 432 nm (excitation light 37
5 nm)).

Example 3 Production and Evaluation of Color Conversion Filter Example 3-1 Production of Color Conversion Filter Using Inorganic Phosphor Ethanol was added to 0.16 g of Aerosil having an average particle size of 5 nm.
5 g and 0.22 g of γ-glycidoxypropyltriethoxysilane were added, and the mixture was stirred for 1 hour at room temperature in an open system. This mixture and (RL-10) 20 prepared in Example 2-1
g was transferred to a mortar and mixed well, and then heated in an oven at 70 ° C. for 2 hours and further in an oven at 120 ° C. for 2 hours to obtain surface-modified (RL-11).

In the same manner, (GL-10) prepared in Example 2-2 and (BL- 10) prepared in Example 2-3.
The surface modification of 3) was also performed. The above surface modification (R
L-11) Butyral (BX-) dissolved in 10 g of a mixed solution (300 g) of toluene / ethanol = 1/1
1) After adding 30 g and stirring, a wet film thickness of 200 μm
Was applied on glass. The coated glass obtained is 10
The color conversion filter (F-1) of the present invention was prepared by heating and drying in an oven at 0 ° C. for 4 hours.

The color conversion filters (F-2) and (BL-) coated with (GL-10) in the same manner.
Color conversion filters (F-3) and (R) coated with 3)
L-12) was applied to prepare a color conversion filter (F-9). (F-1) and (F-9) are 350 to 450 nm
Had an excitation wavelength.

Example 2-2 Preparation of Color Conversion Filter Using Rare Earth Complex Phosphor A mixed solution of toluene / ethanol = 1/1 (300 g)
3 g of the rare earth complex-based phosphor (RE-17) of the present invention is dissolved in 30 g of butyral (BX-1) dissolved in the above step, and coated on a 80 μm-thick polyethersulfone (PES) film at a wet film thickness of 150 μm. After drying with warm air, a color conversion filter (F-4) was prepared.

The color conversion filters (F-5) and (F-5) were produced in the same manner except that RE-17 was replaced with the substances shown in Table 1.
6) was prepared. Example 3-3 Preparation of Color Conversion Filter Using Organic Phosphor A color conversion filter (F-7) was produced in the same manner as in Example 3-2 except that RE-17 was changed to the substances shown in Table 1. ),
(F-8) was created.

[0202]

[Table 1]

Example 3-4 Evaluation of Color Conversion Filter After patterning was performed on a substrate (NA-45, manufactured by NH Techno Glass Co., Ltd.) on which 150 nm of ITO was formed on glass as an anode, a transparent film provided with the ITO transparent electrode was used. The support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while a m-MTD was attached to a molybdenum resistance heating boat.
200 mg of ATXA, 200 mg of the organic compound (VIII-1) in another molybdenum resistance heating boat, and 2 BC in another molybdenum resistance heating boat
00 mg was put in the vacuum evaporation apparatus. Next, after the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, m-MTDATX
The heating boat containing A was energized, heated to 220 ° C., vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec, and a 60-nm-thick hole injection layer was provided. Further, the heating boat containing (VIII-1) was energized and heated to 220 ° C., and the deposition rate was 0.1 to 0.3 nm.
At / sec, a 40 nm-thick light emitting layer was formed by vapor deposition on the hole injection layer. Further, the heating boat containing BC was energized and heated to 250 ° C., and the deposition rate was 0.1 nm /
An electron injection layer having a thickness of 20 nm was formed by vapor deposition on the light emitting layer in sec. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Next, a vacuum chamber was opened, a stainless steel rectangular perforated mask was placed on the electron injection layer, and 3 g of magnesium was put into a molybdenum resistance heating boat.
0.5 g of silver was put into a tungsten evaporation basket, and the pressure in the vacuum chamber was reduced again to 2 × 10 ⁻⁴ Pa.
At 0 nm / sec, magnesium was vapor-deposited. At this time, the silver basket was heated at the same time, and the vapor deposition rate was 0.1 nm / sec.
An electroluminescent element was produced by depositing silver with c to form a counter electrode made of a mixture of magnesium and silver.

Using a color conversion filter (F-1) to (F-9) as a color conversion layer of the organic EL layer, a voltage of DC 8 V was applied to the anode and the cathode. Table 2 shows the values based on the CIE chromaticity coordinates (JIS Z8701) and the emission colors of each color conversion filter at that time.

Further, a luminance of light emitted from the color conversion filter was measured by applying a DC voltage of 12 V in a dry nitrogen gas atmosphere. Next, color conversion filters (F-1) to (F-9) left for 3 days in an environment of 60 degrees and 40%
Then, the color conversion filter irradiated with a xenon fade meter of 100,000 lux for 3 days was allowed to stand, and the luminance emitted from the color conversion filter that had deteriorated in storage was measured.

Table 2 shows the relative values of the respective color conversion filters when the luminance emitted from the color conversion filters that have not deteriorated during storage is set to 100.

[0208]

[Table 2]

[0209] From Table 2, it can be seen that the inorganic phosphor is more excellent in heat stability and light stability than the organic phosphor as a color conversion material. In particular, since the color conversion filters (F-1) and (F-9) of the present invention are extremely excellent in heat stability and light stability, they are very long when used in the color conversion layer of an organic EL device. It is useful because it can have a long life.

Example 4 The electroluminescence device No. Fabrication of Nos. 1 to 34 A methacrylate-based resist containing carbon black (CK200 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is provided on one surface of a non-alkali glass support substrate (7059 manufactured by Corning) having a size of 100 mm × 100 mm × 1.1 mm.
0), and baked at 200 ° C. to about 2 μm
A black solid film having a thickness was formed. Next, the surface of the substrate opposite to the black film was subjected to IPA cleaning and UV cleaning, and then fixed to a substrate holder of a vacuum evaporation apparatus. The evaporation source was m-MTDA as a hole injection material in a molybdenum resistance heating boat.
TXA, the compound (IV-1) of the present invention as a luminescent material, and BC as an electron injecting material were respectively charged. Ag was used as a second metal of the electrode in a tungsten filament, and Mg was used as an electron injecting metal in a molybdenum boat. I attached it. Thereafter, the pressure in the vacuum chamber was reduced to 5 × 10 ⁻⁷ torr,
In a range of 72 mm × 72 mm, an electrode pattern is formed first through a mask capable of forming a film in a 1.5 mm pitch (1.4 mm line, 0.1 mm gap) stripe pattern, and then a 72 mm × 72 mm film is formed. The film from the electron injection layer to the hole injection layer was formed through a mask capable of forming a solid film in the range of. In addition, when the hole injection layer was sequentially laminated from the electrode, it was performed by one evacuation without breaking the vacuum in the middle. First, as electrodes, Mg and Ag were co-evaporated. That is, Mg is deposited at a deposition rate of 1.3 to 1.4 nm /
s and Ag are deposited at a deposition rate of 0.1 nm / s to a thickness of 200 nm.
And Next, as an electron injection layer, BC was deposited at a deposition rate of 0.1 to 0.3 nm / s and a film thickness was 20 nm. As a light emitting layer, an organic compound (IV-1) was deposited at a deposition rate of 0.1 to 0.3 nm / s.
s, a film thickness of 50 nm, and m-MTDA
TXA is deposited at a deposition rate of 0.1 to 0.3 nm / s and a film thickness of 40 n.
m was deposited. Next, this substrate was moved to a sputtering apparatus, and ITO was used as a transparent electrode having a thickness of 120 nm and a resistance of 20 Ω / □ at room temperature, and a 4.5 mm pitch (4.0 mm line, 1.0 mm gap) stripe in a range of 72 mm × 72 mm. The film was formed through a mask capable of forming a film in the shape of an organic EL element. Here,
The electrode and the transparent electrode were crossed, and a mask was arranged so that the terminal of each electrode could be taken. Next, an epoxy-based two-component mixed adhesive (araldide manufactured by CIBA-GEIGY) was applied to the periphery of the intersection (range of 72 mm × 72 mm) of the electrode and the transparent electrode on the substrate by about 1 mm using a dispenser. The coating was performed with a gap in the width. Next, a 100 mm × 100 mm × 0.15 mm non-alkali glass substrate (Corning 7059) was placed on the substrate C.
And the adhesive was cured. Then, under a nitrogen atmosphere, fluorocarbon (Fluorinert manufactured by 3M, USA) was injected with a syringe needle from the gap between the cured adhesive and the gap between the glass substrate bonded to the support substrate. Next, the gap between the adhesives was further filled with the adhesive and cured.

[0211]

Embedded image

On this substrate, a color conversion filter (F-3) as a blue conversion layer, a color conversion filter (F-2) as a green conversion layer, and a color conversion filter (F-1) as a red conversion layer
Are applied at 1.5 mm intervals, and the organic EL element No.
1 was produced.

Further, the organic compound (IV-1) was changed to the compounds shown in Table 3, and the color conversion filters F-1 and F-
Organic EL devices No. 2 to No. 34 were prepared by providing color conversion filters shown in Table 3 as color conversion layers in place of F-2 and F-3.

The band gap was determined by measuring the absorption spectrum of a vapor-deposited film when an organic compound was vapor-deposited on glass at 100 nm, and converting the wavelength at the absorption edge to eV.

[0215]

[Table 3]

The compound not synthesized in Example 1 was synthesized according to the method described in Japanese Patent Application No. 11-341923 and used. Example 5 Organic EL device No. 5 1
Example 5-1 Organic Electroluminescence Device N
o. Evaluation of color conversion efficiency of 1-34 and luminance half-life after continuous light emission Each of the electroluminescent elements No. 1 to NO.34 was continuously lit by applying a 12 V DC voltage in a dry nitrogen gas atmosphere at a temperature of 23 ° C. The luminous efficiency (lm / W) at the start of lighting and the time for halving the luminance are determined by the Minolta C
It measured using S-1000. The luminous efficiency was represented by a relative value when the luminous efficiency of Sample 1 was set to 100, and the time for halving the luminance was represented by a relative value when the time for halving the luminance of Sample 1 was 100. Table 4 shows the results.

[0219]

[Table 4]

From Table 4, it was found that the electroluminescent device of the present invention was excellent in luminous efficiency because an inorganic phosphor was used for the color conversion layer instead of an organic phosphor. In addition, it was found that there is a difference depending on the organic compound in causing the inorganic compound to emit light efficiently. Further, it can be seen that, in the organic EL device of the present invention, the organic compound contained in the light emitting layer has a long life.

Example 5-2 Organic electroluminescent device No. 5 Evaluation of Maximum Achieved Brightness of Organic Electroluminescent Element Nos. 1 to 34 A DC voltage of 10 volts was applied to 1 to 34, and the light emission luminance and the maximum light emission wavelength of each color conversion layer were measured using Minolta CS-1000.
The highest attainable luminance is the same as the organic EL element No. It was expressed as a relative value when the maximum attainable luminance of No. 1 was 100. Table 5 shows the results.
The maximum radiant energy of the light emitting layer was measured before adding the color conversion layer.

[0220]

[Table 5]

As is evident from Table 5, the electroluminescent device of the present invention was found to be very useful as an organic EL device because of its high ultimate luminance. Example 6-1 Organic Electroluminescence Element N
o. Preparation of 6-1 to 6-12 ITO (indium tin oxide) was placed on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode.
Substrate (nm-glass made by NH Techno Glass Co., Ltd. NA-45)
Then, the transparent support substrate provided with the ITO transparent electrode was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus. On the other hand, 200 mg of m-MTDATXA was placed in a molybdenum resistance heating board, and the compound (a) was placed on another molybdenum resistance heating board. And 200 mg of bathocuproine (BC) was placed on another molybdenum resistance heating board, which was then attached to a vacuum evaporation apparatus. Then, the vacuum chamber was set to 4 × 10 ^-4 P
After reducing the pressure to a, the heating board containing m-MTDATXA was energized, heated to 220 ° C., and vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec.
A hole transport layer having a thickness of 33 nm was provided. Further, a current is applied to the heating board containing the compound (a), heated to 220 ° C., and vapor-deposited on the hole transport layer at a vapor deposition rate of 0.1 to 0.3 nm / sec to emit light having a thickness of 33 nm. Layers were provided. The substrate temperature at the time of vapor deposition was room temperature.

Next, a vacuum chamber was opened, a stainless steel rectangular perforated mask was set on the electron injection layer, and 3 g of magnesium was put into a molybdenum resistance heating board.
0.5 g of silver was put into a tungsten basket for vapor deposition, and the pressure in the vacuum chamber was again reduced to 2 × 10 ⁻⁴ Pa.
At 0 nm / sec, magnesium was vapor-deposited. At this time, the silver basket was heated at the same time, and the vapor deposition rate was 0.1 nm / sec.
The organic electroluminescent element 6-1 for comparison was produced by depositing silver with c to form a counter electrode made of a mixture of magnesium and silver.

Organic EL devices 6-2 to 6-14 were manufactured in exactly the same manner as above except that the BC of the electron transport layer was replaced by the compounds shown in Table 6. Example 6-2 Organic electroluminescent device N
o. Evaluation of 6-1 to 6-14 The emission luminances of the samples 6-1 to 6-14 were measured and evaluated.

A voltage was applied to the sample 6-1 and the initial drive voltage 5
At V, current began to flow. The maximum radiant energy of Sample 6-1 was 4 W / Sr · m ² at 9 V. Table 6 shows values (relative values) of the ratios of the maximum radiant energies of the samples 6-1 to 6-14 when the maximum radiant energy of the sample 6-1 at this time is set to 100.

The life test of Sample 6-1 in a nitrogen gas atmosphere showed that the initial radiant energy was 1 W / Sr.
- the half-life of m ² was 840 hours. Table 6 shows values (relative values) of the ratios of the light emission lifetimes of Samples 6-1 to 6-14 when the light emission lifetime of Sample 6-1 is set to 100.

The luminescent color is represented by (x,
y) Determined from coordinates.

[0228]

[Table 6]

As is clear from Table 6, when the organic compound used for the light emitting layer is used for the electron transporting layer, the maximum radiant energy is higher and the light emitting life is longer, so that it is very useful as an organic EL device. It has been found.

Since the luminous efficiency greatly differs depending on the emission color, the comparison was made not by luminance but by radiant energy. Example 7 Production of Organic EL Devices 7-1 to 7-14 and Evaluation of Maximum Achieved Luminance, Luminance Half-Time after Continuous Light Emission On the substrates of Samples 6-1 to 6-14 produced in Example 6-1, A color conversion filter (FB) as a blue conversion layer,
1. A color conversion filter (FG) as a green conversion layer and a color conversion filter (FR) as a red conversion layer.
Samples 7-1 to 7-14 were fabricated by being attached at intervals of 5 mm.

Each of Samples 7-1 to 7-14 was treated at a temperature of 23.
A 9 V DC voltage was applied under an atmosphere of dry nitrogen gas at 9 ° C., and the emission luminance, chromaticity coordinates, and time required to reduce the luminance by half for each of blue, green, and red were measured using Minolta CS-1000. The maximum attainable luminance and the light emission lifetime were represented by relative values when the maximum attainable luminance and light emission life of Sample 7-1 were set to 100. Table 7 shows the results.

[0232]

[Table 7]

As is clear from Table 7, the organic E of the present invention
The L element was found to be very useful as an organic EL element because of the highest attainable luminance and high emission life. Example 8 Organic electroluminescent elements 8-1 to 8-1
Preparation of 8-25 and evaluation of maximum radiant energy and emission lifetime m-MTDATXA having a film pressure of 30 nm was deposited on a transparent support substrate provided with an ITO transparent electrode to form a hole transport layer in the same manner as in Example 6. . On top of this, 40n of compound (a)
m was deposited to form a light emitting layer. Then, on top of that, 30n BC
m to form an electron transport layer. Then Al / L
An organic EL element 8-1 for comparison was prepared by depositing an alloy of i = 99/1 (mass%) with a thickness of 100 nm to form a counter electrode.

A comparative sample 8-2 was prepared in the same manner as in the sample 8-1, except that lithium fluoride was deposited to a thickness of 0.5 nm between the electron transport layer and the aluminum layer to form a cathode buffer layer. did.

In the same manner, the electron transport layer, the light emitting layer, and the cathode buffer layer were structured as shown in Table 8 to obtain a sample 8-
3 to 8-25 were prepared. These elements were heated at a temperature of 23 ° C.
Continuous lighting is performed by applying a DC voltage of 10 V in a dry nitrogen gas atmosphere, and the maximum radiant energy (W / S
rm ² ) and the time to halve the maximum radiant energy were measured. The maximum radiant energy is expressed as a relative value when the maximum radiant energy of 8-1 is set to 100, and the time for halving the maximum radiant energy is the time for halving the maximum radiant energy of sample 8-1. It was expressed as a relative value with the time at which the energy was reduced by half as 100. Table 8 shows the results.

The emission color is represented by (x, y) of the CIE chromaticity coordinates.
Determined from coordinates.

[0237]

[Table 8]

The following can be said from these results. 1) When a cathode buffer layer is laminated, the compound of the present invention is more effective than a conventional compound in which lithium fluoride is laminated.

2) It is more effective to use the organic compound used in the organic EL device of the present invention for the electron transport layer and to further laminate a cathode buffer layer. 3) It is more effective if the organic compound used in the organic EL device of the present invention is used in combination for the electron transport layer and the light emitting layer, and a cathode buffer layer is further laminated.

As a result, an organic EL device which emits blue-violet light and has high luminance and long life was obtained. Example 9 Organic electroluminescent devices 9-1 to 9-1
Preparation of 9-29 and Evaluation of Maximum Luminance and Emission Life In the same manner as in Example 6, m-MTDATXA was deposited on a transparent support substrate provided with an ITO transparent electrode at a film pressure of 30 nm to form a hole transport layer. On top of this, in addition to the compound (a), which is an organic compound, 5% by weight of the fluorescent material (dopant) (DA) was co-deposited at 40 nm with respect to the compound (a) to form a light emitting layer. Subsequently, BC was vapor-deposited thereon to a thickness of 30 nm to form an electron transport layer. Then, add aluminum on top
A comparative sample 9-1 was prepared by vapor-depositing nm to form a counter electrode.

A comparative sample 9 was prepared in the same manner as the sample 9-1 except that lithium fluoride was deposited to a thickness of 0.5 nm between the electron transport layer and the aluminum layer to form a cathode buffer layer.
-2 was produced.

In the same manner, Samples 9-3 to 9-29 were prepared by configuring the electron transport layer, the light emitting layer, the fluorescent material (dopant), and the cathode buffer layer as shown in Table 9.
These samples were heated at a temperature of 23 ° C. in a dry nitrogen gas atmosphere for 1 hour.
Continuous lighting was performed by applying a 0 V DC voltage, and the maximum luminance (cd / m ² ) at the start of the lighting and the time for halving the maximum luminance were measured. The maximum luminance is represented by a relative value when the maximum luminance of 9-1 is set to 100, and the time for halving the maximum luminance is represented by a relative value when the time for halving the maximum luminance of the sample 9-1 is 100. Table 9 shows the results.

[0243]

[Table 9]

The following is clear from these results. 1) It is more effective to use the organic compound used in the organic EL device of the present invention in the electron transport layer and further introduce a dopant into the light emitting layer.

2) The organic E of the present invention is used in the electron transport layer and the light emitting layer.
It is more effective to use an organic compound used in the L element together, further stack a cathode buffer layer, and introduce a dopant into the light emitting layer.

As a result, an organic EL device having high luminance and long life was obtained. Example 10 Organic EL device 10-
Production of 1 to 10-26 and evaluation of maximum radiant energy and emission lifetime In the same manner as in Example 6, on a transparent support substrate provided with ITO transparent electrodes, m-MTDATXA was deposited to a thickness of 30 nm,
The hole transport layer was used. On top of that, 40 nm of TAZ is deposited,
It was a light emitting layer. Subsequently, BC was deposited thereon to a thickness of 30 nm,
An electron transport layer was used. Then Al / Li = 99 /
A comparative sample 10-1 was prepared by depositing 1% (% by mass) of an alloy to a thickness of 100 nm to form a counter electrode.

In the above, sample 1 was prepared in exactly the same manner except that TAZ of the light emitting layer was replaced with a compound shown in Table 10.
0-2 to 10-26 were produced. These elements were heated to a temperature of 2
Continuous lighting was performed by applying a DC voltage of 10 V in a dry nitrogen gas atmosphere at 3 ° C., and the maximum radiant energy (W / Sr · m ² ) at the start of lighting and the time required for halving the maximum radiant energy were measured. The maximum radiant energy is represented by a relative value when the maximum radiant energy of 10-1 is defined as 100,
The time at which the maximum radiant energy was reduced by half was represented by a relative value with the time at which the maximum radiant energy of the sample 10-1 was reduced by half as 100. Table 10 shows the results.

The emission color is represented by (x, y) of the CIE chromaticity coordinates.
Determined from coordinates.

[0249]

[Table 10]

As is clear from Table 10, the organic EL device of the present invention was found to be very useful as an organic EL device because it has a high maximum radiant energy and a long emission life. As a result, an organic EL device emitting blue-violet light with high luminance and long life was obtained.

The comparative sample 10-1 emits blue-violet light, but since the molecular weight is as small as less than 600, the light-emitting compound is degraded by the application of voltage, and the emission life is poor. Was.

Since the luminous efficiency greatly differs depending on the luminescent color, the comparison was made not by luminance but by radiant energy. Example 11 Electroluminescence device No. 11 11
Preparation of -1 to 11-19 and evaluation of maximum radiant energy and emission lifetime m-MTDATXA was deposited to a thickness of 30 nm on a transparent support substrate provided with an ITO transparent electrode in the same manner as in Example 6 to form a hole transport layer. And Compound (a) was deposited thereon to a thickness of 40 nm to form a light emitting layer. Subsequently, BC was vapor-deposited thereon to a thickness of 30 nm to form an electron transport layer. Subsequently, an organic EL element 11-1 for comparison was prepared by depositing an alloy having a weight ratio of aluminum and lithium of 80:20 to 100 nm thereon as a counter electrode.

In the above, the compound (a) of the light emitting layer is shown as
In exactly the same way except that the compound was replaced with the compound shown in 11,
Organic EL devices 11-2 to 11-19 were produced. these
23 ° C in a dry nitrogen gas atmosphere with the element
To perform continuous lighting by applying 10V DC voltage and start lighting
Maximum radiant energy at time (W / sr · m ^Two) And high
The time for halving the radiant energy was measured. Highest radiation
Energy is 100 with the highest radiant energy of 11-1
And halved the maximum radiant energy
Time is when the maximum radiant energy of sample 11-1 is halved
The value was expressed as a relative value with the interval taken as 100.

Further, the samples 11-1 to 11-18 were evaluated in the same manner when the cathode was a counter electrode composed of aluminum / lithium = 99: 1 (mass%). Table 11 shows the results.

[0255]

[Table 11]

The luminescent color is represented by (x,
y) Determined from coordinates. As is clear from Table 11, the electroluminescent device using the compound of the present invention in the light-emitting layer has a high maximum radiant energy and a long light-emitting life, and thus is very useful as an organic EL device. In particular, it was found that when the configuration of the cathode was aluminum / lithium = 99: 1 (% by mass), the emission life was significantly improved.

Since the luminous efficiency greatly differs depending on the emission color, the comparison was made not by luminance but by radiant energy. Example 12 The organic electroluminescent device no.
Evaluation of Maximum Achieved Luminance and Luminance Half-Life Time after Continuous Light Emission of Nos. 12-1 to 12-19 11-1 ~
A color conversion filter (FB) as a blue color conversion layer and a color conversion filter (F
-G), a color conversion filter (FR) was applied as a red conversion layer at intervals of 1.5 mm. 12
-1 to 12-19 were produced.

The cathode was made of aluminum / lithium = 80:
20 (% by mass) and aluminum / lithium = 99: 1
(% By mass) was evaluated as a cathode.

The organic EL device No. 12-1 to 12-19
A DC voltage of 9 V under a dry nitrogen gas atmosphere at a temperature of 23 ° C., to emit blue, green, and red light emission luminance, chromaticity coordinates,
And the time to reduce the luminance by half, CS-1000 manufactured by Minolta
It measured using. The highest attainable brightness and emission life are organic EL
Element No. 12-1 (the cathode is aluminum / lithium =
80:20 (mass%)) and the maximum luminous life is 1
It was expressed as a relative value when 00 was set. Table 12 shows the results.

[0260]

[Table 12]

As is clear from Table 12, the electroluminescent device of the present invention was found to be very useful as an organic EL device because of its highest attainable luminance and long light-emitting life. In particular, it was found that when the configuration of the cathode was aluminum / lithium = 99: 1 (% by mass), the emission life was significantly improved.

[0262]

According to the organic EL device of the present invention, an organic EL device having high luminance, long life and low power consumption can be obtained.

With the organic compound of the present invention, an organic compound which emits blue-violet light with high luminance could be provided. The inorganic phosphor of the present invention can provide an inorganic phosphor that emits red light with an excitation wavelength of 350 to 450 nm and has a long life.

According to the color conversion filter of the present invention, 35
A color conversion filter that emits red light with an excitation wavelength of 0 to 450 nm and has a long life can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing an organic electroluminescence element.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Emission layer 2 Anode 3 Cathode 4 Color conversion layer 5 Glass substrate

FIG. 2 is a diagram showing CIE chromaticity coordinates.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07D 491/048 C07D 491/048 C09K 11/06 640 C09K 11/06 640 650 650 655 655 11/08 11/08 A11 / 59 CPR 11/59 CPR 11/66 CPG 11/66 CPG 11/78 CQD 11/78 CQD H05B 33/02 H05B 33/02 33/12 33/12 EB 33/22 33/22 B 33/26 33 / 26 Z (72) Inventor Yoshiyuki Inuzuri 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo In-house (72) Inventor Noriko Ueda 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo F-term (reference) 3K007 AB02 AB04 AB11 BA06 BB01 BB06 CA01 CB01 DA01 DB03 EB00 4C050 AA01 AA04 BB05 CC05 CC16 EE02 EE04 FF02 FF05 GG01 HH01 4C065 AA05 BB06 CC01 DD03 EE02 HH01 JJ01 KK05 KK09 LL01 PP03 X04 XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA XA

Claims (47)

[Claims] 1. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer has a band gap of 2.96 eV to 3.80 eV and a molecular weight of 600 to 2000. Purp in CIE chromaticity coordinates containing at least one organic compound
light Blue (purple blue) or Blue Pur
An organic electroluminescent device that emits light in ple (blue violet). 2. The organic electroluminescence device according to claim 1, wherein the organic compound has at least one hetero atom in a molecule. 3. The organic electroluminescent device according to claim 1, wherein the organic compound is a heterocyclic compound having at least one hetero atom in a molecule. 4. The band gap of the organic compound is:
The organic electroluminescence device according to any one of claims 1 to 3, wherein the organic electroluminescence device has a voltage of 3.20 eV to 3.60 eV. 5. The organic electroluminescence device according to claim 1, wherein the organic compound is represented by the following general formula (I). Embedded image (Wherein, Z ₁ and Z ₂ are a carbon-carbon single bond or a carbon-carbon double bond and a 5-membered or 6-membered hydrocarbon ring or a heterocyclic ring required to form a heterocyclic ring) Represents a group of non-metallic atoms, provided that Z ₁ and a carbon-carbon single bond or a carbon-carbon double bond, or Z
_At least one of the rings formed by a single bond of ₂ and a carbon-carbon double bond or a carbon-carbon double bond is a heterocyclic ring. R ₁ and R ₂ represent a substituent. When m ₁ + m ₂ ≧ 2, R ₁ and R ₂ may be bonded to each other to form a condensed ring. m ₁ and m ₂ represent an integer of 0 to 6. ) 6. The organic compound according to claim 1, wherein the organic compound is represented by the following general formula (II) or (III).
5. The organic electroluminescence device according to any one of 4. Embedded image (Wherein, Z ₃ , Z ₄ , Z ₅ , and Z ₆ each represent a nonmetallic atom group necessary for forming a 5- or 6-membered aromatic hydrocarbon or a heterocyclic ring. La, Lb, Lc, Ld, Le,
Lf, Lg, Lh, Li, Lj, Lk are -C
(R ₁₀₁ ) =, -N =, -N (R ₁₀₂ )-, -O-, -C
Represents O- or -S-. R ₁₀₁ and R ₁₀₂ represent a hydrogen atom or a substituent. R ₃ , R ₄ , R ₅ and R ₆ represent a substituent. m ₃ , m ₄ , m ₅ , and m ₆ represent an integer of 0 to 6. ) 7. The method according to claim 1, wherein the organic compound is represented by the following general formula (IV):
(V), (VI), (VII), (VIII), (I
X), (X), (XI) or (XII)
The method according to any one of claims 1 to 4, wherein
Electroluminescent element. Embedded image(Where R_a1, R_a2, R_a3, R_a4, R_a5, R_a6, R_a7,
R_a8, R_a9, R_a10, R_{a 11}, R_a12, R_a13, R_a14, R
_a15, R_a16, R_a17, R_a18, And R_a19Are independent
Represents a hydrogen atom or a substituent, and adjacent substituents
Are bonded to each other directly or via a substituent to form a fused ring
May be implemented. R_b1, R_b2, R_b3, R_b4, R _b5, R_b6,
R_b7, R_b8, And R_b9Is an aromatic hydrocarbon, or
Represents a group of nonmetallic atoms necessary for forming a heterocyclic ring. X,
Y is -N (R_a0)-, -C (R_b0R _b1)-,-CO
-, -S-, and -O-. R_a0, R_b0, R_b1Is hydrogen field
Represents a child or a substituent. n₁, N_Two, N_Three, N_Four, N_Five,
n₆, N₇, N₈, And n₉Represents an integer of 0 to 6. ) 8. The method according to claim 1, wherein the organic compound is represented by the following general formula (IV):
(V), (VI), (VII), (VIII), (I
Compounds represented by X), (X), (XI) and (XII)
Each of at least two or more organic compounds selected from
Represented by a compound in which the residues of
The method according to any one of claims 1 to 4, wherein
Organic electroluminescent element. Embedded image(Where R_a1, R_a2, R_a3, R_a4, R_a5, R_a6, R_a7,
R_a8, R_a9, R_a10, R_{a 11}, R_a12, R_a13, R_a14, R
_a15, R_a16, R_a17, R_a18, And R_a19Are independent
Represents a hydrogen atom or a substituent, and adjacent substituents
Are bonded to each other directly or via a substituent to form a fused ring
May be implemented. R_b1, R_b2, R_b3, R_b4, R _b5, R_b6,
R_b7, R_b8, And R_b9Is an aromatic hydrocarbon, or
Represents a group of nonmetallic atoms necessary for forming a heterocyclic ring. X,
Y is -N (R_a0)-, -C (R_b0R _b1)-,-CO
-, -S-, and -O-. R_a0, R_b0, R_b1Is hydrogen field
Represents a child or a substituent. n₁, N_Two, N_Three, N_Four, N_Five,
n₆, N₇, N₈, And n₉Represents an integer of 0 to 6. ) 9. The organic compound represented by the following general formula (XII)
The organic electroluminescent device according to any one of claims 1 to 4, wherein the organic electroluminescent device is represented by (I), (XIV), or (XV). Embedded image (Wherein, Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z
₁₄ and Z _{15 each} represent a residue of the organic compound represented by any one of the general formulas (IV) to (XII). _Lx , _Ly , and _Lz each represent a divalent, trivalent, or tetravalent linking group. ) 10. An organic electroluminescent device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVI). Embedded image (In the formula, R _c1 , R _c2 , and R _c3 each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ , and X ₃ represent —NR _d —, an oxygen atom, or a sulfur atom. ₁ , L ₂ and L ₃ represent a linking group having a π bond, R _d represents an alkyl group, an aryl group,
Represents a substituted alkyl group or a substituted aryl group. k ₁ , k ₂ , k
₃ represents an integer of 0 to 6. ) 11. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVII). Embedded image .L representing the oxygen atom or a sulfur atom - _{(wherein, R e1, R e2, R} e3 .X 4, X 5, X 6 representing a each independently represent a hydrogen atom or a substituent, -NR _{f 4, L} 5, _{L 6} is .R _f is an alkyl group represented linking group having a bond [pi, aryl group, substituted alkyl group, .k ₄ to a substituted aryl group,
k ₅ and k ₆ represent an integer of 0 to 6. ) 12. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XVIII). Embedded image (In the formula, R _g1 , R _g2 , and R _g3 each independently represent a hydrogen atom or a substituent. X ₇ , X ₈ , and X ₉ represent —NR _h —, an oxygen atom, or a sulfur atom. ₇ , L ₈ and L ₉ each represent a linking group having a π bond, and R _h represents an alkyl group, an aryl group,
Represents a substituted alkyl group or a substituted aryl group. k _7, k _8, k
₉ represents an integer of 0 to 6. ) 13. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer contains an organic compound represented by the following general formula (XIX). Embedded image (Wherein, R _i1 , R _i2 , R _i3 , R _j1 , R _j2 , and R _j3 each independently represent a hydrogen atom or a substituent. X ₁₀ , X ₁₁ , X
₁₂ represents —NR _k —, an oxygen atom, or a sulfur atom. R _k represents an alkyl group, an aryl group, a substituted alkyl group,
Represents a substituted aryl group. k ₁₀ , k ₁₁ and k ₁₂ represent an integer of 0 to 6. ) 14. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, wherein the light emitting layer has the following general formula (XX-1), (XX-2),
An organic electroluminescence device containing at least one of the organic compounds represented by (XX-3) or (XX-4). Embedded image ( _Where R _k1 , R _k2 , R _k3 , R _k4 , R _k5 , R _k6 , R _k7 ,
_{R k8, R l1, R l2} , R l3, R l4, R l5, R l6, R l7, R
_{l8, R m1, R m2,} R m3, R m4, R m5, R m6, R m7,
_{R m8, R n1, R n2} , R n3, R n4, R n5, R n6, R n7, R
_n8 each independently represents a hydrogen atom or a substituent. ) 15. The organic compound according to claim 2, wherein the organic compound is 2.96 to 3.80.
The organic electroluminescence device according to any one of claims 10 to 14, wherein the organic electroluminescence device has a band gap in an eV range. 16. The organic compound according to claim 3, wherein the organic compound is 3.20 eV to 3.20 eV.
The organic electroluminescence device according to any one of claims 10 to 14, wherein the organic electroluminescence device has a band gap in a range of 60 eV. 17. The organic compound having a molecular weight of 600 to 2
The organic electroluminescent device according to any one of claims 10 to 16, wherein the molecular weight is 000. 18. The method according to claim 1, further comprising an electron transport layer for transporting electrons from the cathode, wherein the electron transport layer contains at least one kind of the organic compound. Organic electroluminescent element. 19. The organic electroluminescent device according to claim 1, further comprising at least one cathode buffer layer between said cathode and said light emitting layer. 20. The organic electroluminescence device according to claim 1, wherein the cathode has an aluminum content of 90% by mass or more and less than 100% by mass. 21. The organic electroluminescent device according to claim 1, further comprising a color conversion layer containing at least one phosphor. 22. The organic electroluminescent device according to claim 21, wherein the phosphor is an inorganic phosphor. 23. The color conversion layer, which absorbs at least light having a maximum emission wavelength of the organic compound and has a wavelength of 400 to 50.
A conversion layer containing at least one inorganic phosphor having a maximum emission wavelength in the range of 0 nm; and an inorganic layer having a maximum emission wavelength in the range of 501 to 600 nm by absorbing light of the organic compound at the maximum emission wavelength. A conversion layer containing at least one kind of phosphor based on the organic compound, and a conversion layer containing at least one kind of inorganic phosphor having a maximum emission wavelength in the range of 601 to 700 nm by absorbing light having a maximum emission wavelength of the organic compound. The organic electroluminescence device according to claim 21, comprising: 24. The inorganic phosphor of the following general formula (A)
The organic electroluminescent device according to claim 22, wherein: General formula (A) M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2z is satisfied. n may be 0. ) 25. The organic electroluminescent device according to claim 24, wherein in the general formula (A), M is magnesium. 26. The inorganic phosphor of the following general formula (B)
The organic electroluminescent device according to claim 22, wherein: Formula _{(B) N u Eu y (} W 1-t Mo t O 4) w ( however, M is an alkaline earth metal, 2W = u + 3
v, and t is an integer of 0 or 1. ) 27. In the general formula (B), N is potassium and t is 0.
3. The organic electroluminescent device according to 1.). 28. The organic electroluminescence device according to claim 22, wherein the inorganic phosphor is a rare earth complex phosphor. 29. The method according to claim 29, wherein the inorganic phosphor is Sol-Gel.
29. The method according to claim 22, wherein the element is manufactured by a method.
The organic electroluminescent device according to any one of the above. 30. An organic compound represented by the following general formula (XVI). Embedded image (In the formula, R _c1 , R _c2 , and R _c3 each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ , and X ₃ represent —NR _d —, an oxygen atom, or a sulfur atom. ₁ , L ₂ and L ₃ represent a linking group having a π bond, R _d represents an alkyl group, an aryl group,
Represents a substituted alkyl group or a substituted aryl group. k ₁ , k ₂ , k
₃ represents an integer of 0 to 6. ) 31. An organic compound represented by the following general formula (XVII). Embedded image .L representing the oxygen atom or a sulfur atom - _{(wherein, R e1, R e2, R} e3 .X 4, X 5, X 6 representing a each independently represent a hydrogen atom or a substituent, -NR _{f 4, L} 5, _{L 6} is .R _f is an alkyl group represented linking group having a bond [pi, aryl group, substituted alkyl group, .k ₄ to a substituted aryl group,
k ₅ and k ₆ represent an integer of 0 to 6. ) 32. An organic compound represented by the following general formula (XVIII). Embedded image (In the formula, R _g1 , R _g2 , and R _g3 each independently represent a hydrogen atom or a substituent. X ₇ , X ₈ , and X ₉ represent —NR _h —, an oxygen atom, or a sulfur atom. ₇ , L ₈ and L ₉ each represent a linking group having a π bond, and R _h represents an alkyl group, an aryl group,
Represents a substituted alkyl group or a substituted aryl group. k _7, k _8, k
₉ represents an integer of 0 to 6. ) 33. An organic compound represented by the following general formula (XIX). Embedded image (Wherein, R _i1 , R _i2 , R _i3 , R _j1 , R _j2 , and R _j3 each independently represent a hydrogen atom or a substituent. X ₁₀ , X ₁₁ , X
₁₂ represents —NR _k —, an oxygen atom, or a sulfur atom. R _k represents an alkyl group, an aryl group, a substituted alkyl group,
Represents a substituted aryl group. k ₁₀ , k ₁₁ and k ₁₂ represent an integer of 0 to 6. ) 34. The following general formulas (XX-1) and (XX-
2) An organic compound represented by (XX-3) or (XX-4) ( _Where R _k1 , R _k2 , R _k3 , R _k4 , R _k5 , R _k6 , R _k7 ,
_{R k8, R l1, R l2} , R l3, R l4, R l5, R l6, R l7, R
_{l8, R m1, R m2,} R m3, R m4, R m5, R m6, R m7,
_{R m8, R n1, R n2} , R n3, R n4, R n5, R n6, R n7, R
_n8 each independently represents a hydrogen atom or a substituent. ) 35. The semiconductor device according to claim 30, having a band gap in a range of 2.96 to 3.80 eV.
4. The organic compound according to any one of 4. 36. The semiconductor device according to claim 30, having a band gap in a range of 3.20 to 3.60 eV.
4. The organic compound according to any one of 4. 37. The compound of the above formula having a molecular weight of 600 to 200.
The organic compound according to any one of claims 30 to 36, which is within a range of 0. 38. An inorganic phosphor represented by the following general formula (A). General formula (A) M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2z is satisfied. n may be 0. ) 39. A color conversion filter comprising at least one compound represented by the following general formula (A). General formula (A) M _x Ge _y O _z F _n : Mn _m ⁴⁺ (where M is an alkaline earth metal and n = 2x + 4
It is assumed that (y + m) -2z is satisfied. n may be 0. ) 40. The color conversion filter according to claim 39, wherein M in the general formula (A) is magnesium. 41. The formula (A) is a Sol-Gel
39. The method according to claim 39 or claim 4, wherein the element is manufactured by a method.
0. The color conversion filter according to 0. 42. An organic electroluminescence device having a cathode, an anode, and a light emitting layer, comprising an organic compound having a band gap of 2.96 eV to 3.80 eV, a phosphor, and 450 to 700 nm.
An organic electroluminescent device having at least one maximum emission wavelength within the range of. 43. The organic electroluminescence device according to claim 42, wherein the light emitting layer contains the organic compound and the phosphor. 44. The organic compound having a molecular weight of 600 to 2
The organic electroluminescence device according to claim 42 or 43, wherein the number is 000. 45. The organic compound according to claim 4, wherein the organic compound has at least one hetero atom in the molecule.
45. The organic electroluminescent device according to any one of 2 to 44. 46. The organic electroluminescent device according to claim 42, wherein the organic compound is a heterocyclic compound having at least one hetero atom in a molecule. 47. The organic electroluminescent device according to claim 42, wherein the band gap of the organic compound is 3.20 eV to 3.60 eV.