JP2002226484A - Coumarin derivative, method for producing the same, and luminescent agent and light emitting device utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional organic material useful as an agent for photoabsorption, and a luminescent agent and to provide applications thereof. SOLUTION: This coumarin derivative has a specific structure and properties. The agent for the photoabsorption and the luminescent agent contain the coumarin derivative. The organic electroluminescence element and applications thereof use the coumarin derivative. The method for producing the coumarin derivative comprises a step for reacting the coumarin compound having an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions of the coumarin skeleton respectively, and a juloidine skeleton at the position except the 3- and 4-position thereof, with a hydrocarbon having a thiol group and a primary amino group at the neighboring carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coumarin derivative, and more particularly to a coumarin derivative useful in an organic electroluminescent device (hereinafter abbreviated as "organic EL device").

[0002]

[Prior Art] With the arrival of the multimedia age,
Organic EL elements have been spotlighted as next-generation display elements. At present, cathode ray tubes are mainly used in relatively large information display devices such as computer terminals and televisions. However, since the CRT is large in volume and weight and has a high operating voltage, it is not suitable for consumer devices and small devices that emphasize portability. There is a need for smaller devices that are thinner, lighter in panel shape, have lower operating voltages, and consume less power. At present, a liquid crystal element has a low operating voltage and a relatively low power consumption, and is frequently used in various fields. However, information display devices using liquid crystal elements vary in contrast depending on the viewing angle, so that a clear display cannot be obtained unless reading is performed within a certain angle range.
Since a backlight is required, there is a problem that power consumption is not so reduced. An organic EL element has emerged as a display element that solves these problems.

[0003] An organic EL device usually has a light-emitting layer containing a light-emitting compound interposed between an anode and a cathode, and a direct-current voltage is applied between the anode and the cathode to form holes in the light-emitting layer. A light-emitting element that uses light emission such as fluorescence or phosphorescence emitted when the excited state returns to the ground state by creating an excited state of the luminescent compound by injecting electrons and recombining them with each other. is there. Organic EL elements
In forming the light emitting layer, by selecting an appropriate compound as the host compound and changing the guest compound (dopant) to be combined with the host compound,
There is a feature that the color tone of light emission can be appropriately changed. Also, depending on the combination of the host compound and the guest compound,
There is a possibility that the brightness and life of light emission can be significantly improved. In the first place, an organic EL element emits light by itself, and an information display device using the organic EL element has an advantage that it has no viewing angle dependence and does not require a backlight, so that power consumption can be reduced. Is said to be.

However, the organic EL devices proposed so far
Many of the elements have low durability. For example, when used in a severe environment such as mounting on a vehicle where vibration and high temperature are unavoidable, there is a problem that the luminance is reduced in a short time.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a functional organic material useful as a light absorbing agent and a luminescent agent, particularly a luminescent material useful in an organic EL device aiming at high durability. It is to provide an organic compound and its use.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with a focus on coumarin derivatives and searched for a hydrocarbon group bonded to the 4-position in the coumarin skeleton, and a site other than the 4-position. A coumarin derivative having a urolidine skeleton and a benzothiazole skeleton emits visible light having a relatively long wavelength in an organic EL device, in particular, visible light in a green range or a red range. I found it to last. Further, such a coumarin derivative has an absorption maximum in a visible region and also has a property of substantially absorbing visible light, so that it can be used as a light absorber and a luminescent agent in addition to the field of organic EL devices. Require an organic compound having such properties, for example, photochemical polymerization,
It has been found that it can be advantageously used in various fields including solar cells, dyeing, optical filters, dye lasers and the like.

[0007] That is, the present invention solves the above-mentioned problem by combining a coumarin skeleton with a hydrocarbon group at the 4-position,
In addition, the problem is solved by providing a coumarin derivative having a urolidine skeleton and a benzothiazole skeleton at a site other than the 4-position.

[0008] Further, the present invention solves the above-mentioned problems by providing a light absorber comprising such a coumarin derivative.

Further, the present invention solves the above-mentioned problems by providing a luminescent agent containing such a coumarin derivative.

Further, the present invention solves the above-mentioned problems by providing an organic EL device using such a coumarin derivative.

Further, the present invention solves the above-mentioned problems by providing an organic EL element using such a coumarin derivative in a display panel.

Further, the present invention solves the above-mentioned problems by providing an organic EL element using such a coumarin derivative for use in an information display device.

Further, the present invention solves the above-mentioned problem by providing an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions of the coumarin skeleton, respectively, and having a urolidine skeleton at a site other than the 3- and 4-positions. The problem is solved by providing a method for producing a coumarin derivative via a step of reacting a compound with an aromatic hydrocarbon in which a thiol group and a primary amino group are bonded to adjacent carbon atoms.

Most of the coumarin derivatives of the present invention show a glass transition point around 100 to 110 ° C.
In recent studies on organic EL devices, it is said that it is essential to use a light-emitting compound having a high glass transition point in order to produce a highly durable organic EL device. In view of such research trends, it is possible to produce an organic EL device having good durability depending on the structure of the luminescent compound even if the compound is a luminescent compound having a low glass transition point such as the coumarin derivative according to the present invention. It was a completely unexpected discovery.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a coumarin derivative having a hydrocarbon group bonded to the 4-position of a coumarin skeleton and having a urolidine skeleton and a benzothiazole skeleton at a position other than the 4-position. Further, the present invention viewed from another viewpoint also relates to a coumarin derivative having a light emission maximum in a visible region and having a glass transition point in a range of 100 to 110 ° C. According to the present invention, as described above, such a coumarin derivative has an absorption maximum in the visible region and, in addition to substantially absorbing visible light, has a light emission maximum such as a fluorescence maximum in the visible region, and is excited. Then, it is based on the unique finding that the light emits visible light of a relatively long wavelength, particularly, visible light of a green to red range.
Therefore, any coumarin derivative can be advantageously used in accordance with the present invention as long as it has such structure and / or physical properties. The emission maximum wavelength of the coumarin derivative can be determined by an ordinary method, for example, by measuring an emission spectrum or a phosphorescence spectrum, and the glass transition point can be determined by, for example, a general-purpose differential scanning calorimetry (hereinafter, “DSC analysis”). .).

An example of such a coumarin derivative is, for example, one represented by the general formula 1.

[0017]

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In the general formula 1, R ₁ represents a hydrocarbon group, and the hydrocarbon group may have one or more substituents. Examples of the hydrocarbon group for R ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, -Butenyl group, up to 5 carbon atoms such as 1,3-butadienyl group,
Usually, an alicyclic hydrocarbon group such as an aliphatic hydrocarbon group having 1 to 4 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, o-tolyl group, m-tolyl Group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m
And aromatic hydrocarbon groups such as -cumenyl group, p-cumenyl group and diphenylyl group. One or more of the hydrogen atoms in such a hydrocarbon group is, for example, a methoxy group, a trifluoromethoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group,
ether groups such as sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, phenoxy group, benzyloxy group, acetoxy group, trifluoroacetoxy group, benzoyloxy group, methoxycarbonyl group, trifluoromethoxycarbonyl Group, ethoxycarbonyl group, ester group such as propoxycarbonyl group, further, fluoro group, chloro group, bromo group,
It may be substituted by a halogen group such as an iodine group.

R _{2 to} R ₅ in the general formula 1 each independently represent a hydrogen atom or an aliphatic hydrocarbon group. As the aliphatic hydrocarbon group for R _{2 to} R _5, up to 5 carbon atoms, usually 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- Examples thereof include a butyl group and a tert-butyl group. Varying depending on the application, the preferred organic EL element, all R ₂ to R ₅ are coumarin derivatives is an aliphatic hydrocarbon group, especially, a coumarin derivative R ₂ to R ₅ are all methyl groups It is particularly excellent in physical properties and economy.

Z in the general formula 1 represents an aromatic ring fused to a thiazole ring. As individual aromatic rings, for example,
Examples include monocyclic hydrocarbons such as benzene, condensed polycyclic hydrocarbons such as naphthalene, anthracene, phenanthrene, naphthacene, and chrysene, and ring-assembled hydrocarbons such as biphenyl, terphenyl, phenylnaphthalene, and naphthylnaphthalene.

Specific examples of the coumarin derivative according to the present invention include those represented by Chemical Formulas 1 to 27. Each of these has an absorption maximum in the visible region and, in addition to substantially absorbing visible light,
It has a light emission maximum such as a fluorescence maximum in a visible region, and in particular, an organic EL element has a remarkable property of stably sustaining light emission in a green range or a red range for a long time.

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[0048]

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The coumarin derivative according to the present invention can be prepared by various methods. However, if economical importance is attached, for example, an aldehyde group and a hydrocarbon group are bonded to the coumarin skeleton at the 3- and 4-positions, respectively. , 3rd and 4th
Via a step of reacting a compound having a urolidine skeleton at a position other than the position with a monocyclic, fused polycyclic or ring-assembled hydrocarbon in which a thiol group and a primary amino group are bonded to adjacent carbon atoms. Is preferred. According to this method, for example, a compound represented by General Formula 2 having R _{1 to} R ₅ corresponding to General Formula 1 is reacted with a compound represented by General Formula 3 having Z corresponding to General Formula 1. By doing so, the coumarin derivative of the present invention is produced in good yield.

[0050]

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[0051]

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That is, an appropriate amount of each of the compounds represented by the general formulas 2 and 3 is added to a reaction vessel (usually about equimolar), and if necessary, dissolved in an appropriate solvent. Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N
Basic compounds such as N-diethylaniline, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acetic anhydride and other acidic compounds, aluminum chloride, zinc chloride, After adding a Lewis acidic compound such as tin tetrachloride or titanium tetrachloride, the mixture is reacted at ambient temperature or a temperature higher than ambient temperature with stirring by heating under reflux or the like.

Examples of the solvent include pentane, hexane, cyclohexane, octane, benzene, toluene,
Hydrocarbons such as xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, halides such as α-dichlorobenzene, methanol, ethanol, 1- Propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene Alcohols such as ethylene glycol and glycerin and phenols, diethyl ether, diisopropyl ether, tetrahydrofuran, tetra Doropiran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl -
Ethers such as 18-crown-6, methyl carbitol, ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N- Acids and acid derivatives such as methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, nitriles such as acetonitrile, propionitrile, succinonitrile, benzonitrile, and nitromethane And nitro compounds such as nitrobenzene; sulfur-containing compounds such as dimethylsulfoxide and sulfolane; water; and the like, if necessary.

When a solvent is used, the efficiency of the reaction generally decreases with an increase in the amount of the solvent, and conversely, with a decrease in the amount of the solvent, it becomes difficult to uniformly heat and stir or a side reaction easily occurs. Accordingly, it is desirable that the amount of the solvent be 100 times, usually 5 to 50 times, the weight of the whole starting compound. The reaction is completed within 10 hours, usually 0.5 to 5 hours, depending on the type of the starting compound and the reaction conditions. The progress of the reaction can be monitored by a general-purpose method such as thin-layer chromatography, gas chromatography, and high-performance liquid chromatography. Coumarin derivatives represented by Chemical Formulas 1 to 27 can all be produced in desired amounts by this method. Incidentally, all of the compounds represented by the general formulas 2 and 3 can be obtained by a general-purpose method for preparing an analogous compound, and when a commercially available product is available, it may be used as it is.

The coumarin derivative thus obtained is usually used prior to use, for example, dissolution, extraction, separation, gradient, filtration, concentration, thin-layer chromatography, column chromatography, gas chromatography, high-performance liquid chromatography. Purification is performed by general-purpose methods for purifying analogous compounds such as chromatography, distillation, sublimation, and crystallization, and these methods are applied in combination as necessary. Although it depends on the use of the coumarin derivative, when it is used for an organic EL device or a dye laser, it is desirable that the coumarin derivative be highly purified before use, for example, by a method such as distillation, crystallization and / or sublimation. Of these, sublimation is particularly excellent because high-purity crystals can be easily obtained in a single operation, the loss of the coumarin derivative accompanying the operation is small, and no solvent is taken into the crystals. I have. The sublimation method to be applied may be a normal pressure sublimation method or a reduced pressure sublimation method, but usually the latter reduced pressure sublimation method is employed. To sublimate the coumarin derivative of the present invention under reduced pressure, for example,
An appropriate amount of a coumarin derivative is charged into a sublimation purification apparatus, and the pressure inside the apparatus is reduced to less than 10 ^-2 Torr, specifically 10 ^-3 T
While maintaining the temperature at orr or lower, the coumarin derivative is heated at a temperature as low as possible, desirably below the melting point, so as not to decompose. When the purity of the coumarin derivative to be subjected to the sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of decompression or the heating temperature so that impurities are not mixed, and when the coumarin derivative is difficult to sublimate,
Sublimation is promoted by passing an inert gas such as a rare gas into the sublimation purification device. The size of the crystals obtained by sublimation can be adjusted by adjusting the temperature of the condensing surface in the sublimation refining device, and by keeping the condensing surface at a temperature slightly lower than the heating temperature and gradually crystallizing. Relatively large crystals are obtained.

The use of the coumarin derivative according to the present invention will be described. As described above, the coumarin derivative according to the present invention has an absorption maximum in the visible region and substantially absorbs visible light. Since it has the property of emitting a visible light when excited when it has an emission maximum, it can be used as a light absorbing agent and a luminescent agent in various fields requiring organic compounds having such properties. Having. One of the most important uses is a use as a functional organic material in organic electronics, particularly, a use as a light emitting layer material in an organic EL device.

Therefore, first, the use of the coumarin derivative according to the present invention in an organic EL device will be described. The organic EL device according to the present invention means the general electroluminescent device using the coumarin derivative as described above. An anode to which a positive voltage is applied, a cathode to which a negative voltage is applied, a light-emitting layer for extracting light emission by recombining holes and electrons, and, if necessary, a hole for injecting and transporting holes from the anode. A single layer including an injection / transport layer, an electron injection / transport layer that injects and transports electrons from the cathode, and a hole blocking layer that suppresses holes from moving from the light-emitting layer to the electron injection / transport layer. And multilayer organic EL devices are important applications.

As is well known, the operation of an organic EL device essentially consists of a process of injecting electrons and holes from an electrode, a process of moving electrons and holes through a solid, and a recombination of electrons and holes. However, the process includes a process of generating a singlet or triplet exciton and a process of emitting the exciton, and there is no difference between the single-layer organic EL device and the stacked organic EL device. However, in the single-layer organic EL device, the characteristics of the above four steps can be improved only by changing the structure of the light-emitting compound, whereas in the stacked organic EL element, it is required in each step. Since functions can be shared among multiple materials and each material can be independently optimized, it is generally better to configure a stacked type rather than a single layer type to achieve the desired performance. Easy to achieve.

Therefore, the organic EL device of the present invention
To further explain, taking a stacked organic EL element as an example, FIG. 1 is a schematic view of a stacked organic EL element according to the present invention, in which 1 is a substrate, usually soda glass, barium silicate glass, Glass such as aluminosilicate glass, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
Plastics such as polyethylene, quartz, general-purpose substrate materials including ceramics such as ceramics are used in the form of a plate, sheet or film, and if necessary,
These are appropriately laminated and used. Preferred substrate materials are transparent glass and plastic, and opaque ceramics such as silicon are used in combination with transparent electrodes. When it is necessary to adjust the chromaticity of light emission,
Chromaticity adjusting means such as a filter film, a chromaticity conversion film, and a dielectric reflection film are provided at appropriate places.

Reference numeral 2 denotes an anode, which is formed by depositing one or more of a metal or a conductive compound having a low electrical resistivity and a large light transmittance over the entire visible region, for example, by vacuum evaporation or sputtering. The substrate 2 is brought into close contact with one side of the substrate 1 by a method such as chemical vapor deposition (CVD), atomic layer epitaxy (ALE), coating, or dipping, so that the resistivity at the anode 2 is 1 k.
It is formed by forming a single layer or a multilayer having a thickness of 10 to 1,000 nm, desirably 50 to 500 nm so as to be Ω / □ or less, preferably 5 to 50 Ω / □. Examples of the conductive material in the anode 2 include metals such as gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, and aluminum, zinc oxide, tin oxide, indium oxide, and tin oxide and indium oxide. Examples thereof include metal oxides such as a mixed system (hereinafter, abbreviated as “ITO”), and conductive oligomers and conductive polymers having aniline, thiophene, pyrrole, and the like as repeating units. Of these, ITO
Is characterized in that a material having a low resistivity can be easily obtained, and a fine pattern can be easily formed by etching using an acid or the like.

Reference numeral 3 denotes a hole injecting / transporting layer, which is usually an anode
2 in the same manner as in 2,
The hole injection / transport layer material is manufactured to a thickness of 1 to 1,000 nm.
It is formed by filming. Material for hole injection / transport layer
The hole injection and transport from the anode 2
In order to minimize the ionization potential, ^Four
To 10⁶Under an electric field of V / cm, at least 1
0^-6cm^Two/ V · s exhibiting hole mobility is desirable
New Organic EL is used as a material for each hole injection / transport layer.
Commonly used in devices, for example, arylamine derivatives
Body, imidazole derivative, oxadiazole derivative,
Xazole derivatives, triazole derivatives, chalcone derivatives
Body, styryl anthracene derivative, stilbene derivative,
Tetraarylethene derivatives, triarylamine derivatives
, Triarylethene derivatives, triarylmethane derivatives
Conductor, phthalocyanine derivative, fluorenone derivative,
Drazone derivative, N-vinyl carbazole derivative, pyra
Zoline derivative, pyrazolone derivative, phenylanthrace
Derivatives, phenylenediamine derivatives, polyaryls
Lucane derivative, polysilane derivative, polyphenylene vinyl
And derivatives thereof, if necessary.
Used in any combination.

Reference numeral 4 denotes a light emitting layer, which is usually brought into close contact with the hole injecting / transporting layer 3 in the same manner as in the anode 2, and one or more of the coumarin derivatives according to the present invention, if necessary, And a single layer or a multi-layer, and each is formed into a film having a thickness of 10 to 1,000 nm, preferably 10 to 200 nm. When used in combination with a host compound, the coumarin derivative according to the present invention is added to the host compound in an amount of 0.05%.
To 50% by weight, preferably 0.1 to 30% by weight.

When the coumarin derivative according to the present invention is used as a guest compound, the other luminescent compound to be combined with the coumarin derivative according to the present invention, that is, as the host compound, a quinolinol metal complex commonly used in organic EL devices, for example, Anthracene, chrysene, coronene,
Condensed polycyclic aromatic hydrocarbons such as triphenylene, naphthacene, naphthalene, phenanthrene, picene, pyrene, fluorene, perylene, benzopyrene and derivatives thereof, quarterphenyl, 1,4-diphenylbutadiene, terphenyl, stilbene, tetraphenylbutadiene , Biphenyl and other ring-assembled hydrocarbons and their derivatives, carbazole and other heterocyclic compounds and their derivatives, quinacridone, rubrene, and styryl-based polymethine dyes.

A preferred host compound is a quinolinol metal complex. The quinolinol metal complex referred to in the present invention has a pyridine residue and a hydroxy group in the molecule.
For example, 8-quinolinols, benzoquinoline-10-
Quinolinols as ligands such as ols, and the formation of a coordination bond with the ligand by donating an electron pair from the nitrogen atom in the pyridine residue, as a central atom, for example, lithium, beryllium, Group 1, Group 2, Group 12, or Group 13 in the periodic table of magnesium, calcium, zinc, aluminum, gallium, indium, etc.
It generally means a complex comprising a metal belonging to the group or an oxide thereof. When the ligand is any of 8-quinolinols or benzoquinolin-10-ol, they may have one or more substituents, other than carbon at the 8- or 10-position to which the hydroxy group is bonded. To the carbon, for example, a fluoro group, a chloro group, a bromo group, a halogen group such as an iodo group, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
sec-butyl group, tert-butyl group, pentyl group,
Aliphatic hydrocarbon groups such as isopentyl group, neopentyl group and tert-pentyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group Group, pentyloxy group, isopentyloxy group, phenoxy group, ether group such as benzyloxy group, acetoxy group, trifluoroacetoxy group, benzoyloxy group, methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl It does not prevent an ester group such as a group, or a substituent such as a cyano group, a nitro group or a sulfo group from binding to one or more. When the quinolinol metal complex has two or more ligands in the molecule, those ligands may be the same or different from each other.

Examples of the individual quinolinol metal complexes include tris (8-quinolinolate) aluminum, tris (3,4-dimethyl-8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (4 -Methoxy-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, tris (5-
Chloro-8-quinolinolate) aluminum, tris (5-bromo-8-quinolinolate) aluminum, tris (5,7-dichloro-8-quinolinolate) aluminum, tris (5-cyano-8-quinolinolate) aluminum, tris (5- Aluminum complexes such as sulfonyl-8-quinolinolate) aluminum, tris (5-propyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) aluminum oxide, bis (8-quinolinolate) zinc, bis (2-
Methyl-8-quinolinolate) zinc, bis (2,4-dimethyl-8-quinolinolate) zinc, bis (2-methyl-5-chloro-8-quinolinolate) zinc, bis (2-
Methyl-5-cyano-8-quinolinolate) zinc, bis (3,4-dimethyl-8-quinolinolate) zinc, bis (4,6-dimethyl-8-quinolinolate) zinc, bis (5-chloro-8-quinolinolate) Zinc, screw (5
Zinc complexes such as 7-dichloro-8-quinolinolate) zinc, bis (8-quinolinolate) beryllium, bis (2
-Methyl-8-quinolinolate) beryllium, bis (2,4-dimethyl-8-quinolinolate) beryllium, bis (2-methyl-5-chloro-8-quinolinolate) beryllium, bis (2-methyl-5-cyano-8) −
Quinolinolate) beryllium, bis (3,4-dimethyl-8-quinolinolate) beryllium, bis (4,6-dimethyl-8-quinolinolate) beryllium, bis (5-
Chloro-8-quinolinolate) beryllium, bis (5,
Beryllium complexes such as 7-dichloro-8-quinolinolate) beryllium, bis (10-hydroxybenzo [h] quinolinolate) beryllium, bis (8-quinolinolate) magnesium, bis (2-methyl-8-quinolinolate) magnesium, bis (2 , 4-Dimethyl-8-quinolinolate) magnesium, bis (2-methyl-5-
Chloro-8-quinolinolate) magnesium, bis (2
-Methyl-5-cyano-8-quinolinolate) magnesium, bis (3,4-dimethyl-8-quinolinolate)
Magnesium, bis (4,6-dimethyl-8-quinolinolate) magnesium, bis (5-chloro-8-quinolinolate) magnesium, bis (5,7-dichloro-8)
-Quinolinolato) magnesium complex such as magnesium, indium complex such as tris (8-quinolinolato) indium, gallium complex such as tris (5-chloro-8-quinolinolato) gallium, bis (5-chloro-
Examples thereof include calcium complexes such as 8-quinolinolate) calcium, and these may be used in an appropriate combination as necessary. The host compounds described above are merely examples, and the host compounds used in the present invention should not be limited to these.

Reference numeral 5 denotes an electron injecting / transporting layer, which is usually brought into close contact with the light emitting layer 4 in the same manner as in the anode 2 to form an organic compound having a high electron affinity or a cyclic compound such as benzoquinone, anthraquinone, or fluorenone. One or more of a conductive oligomer or a conductive polymer having a repeating unit of a ketone or a derivative thereof, a silazane derivative, and aniline, thiophene, pyrrole, or the like, has a thickness of 1 or more.
It is formed by forming a film with a thickness of 0 to 500 nm.
When a plurality of materials for the electron injection / transport layer are used, even if the plurality of materials for the electron injection / transport layers are uniformly mixed and formed into a single layer, each material for the electron injection / transport layer is mixed without mixing. It may be formed in a plurality of adjacent layers. When the hole blocking layer is provided, prior to the formation of the electron injection / transport layer 5, the hole blocking layer is brought into close contact with the light emitting layer 4 in the same manner as in the anode 2, for example, 2-biphenyl-4-yl-5-
(4-tert-butyl-phenyl)-[1,3,4]
Oxadiazole, 2,2-bis [5- (4-biphenyl) -1,3,4-oxadiazol-2-yl-1,
4-phenylene] hexafluoropropane, 1,3,5
-Tris- (2-naphthalen-1-yl- [1,3,
4] A thin film is formed using a hole blocking material including an oxadiazole-based compound such as oxadiazol-5-yl) benzene. The thickness of the hole blocking layer is 1 to 100 nm, usually 10 to 50, while taking into consideration the thickness of the electron injection / transport layer 5 and the operating characteristics of the organic EL device.
Set in the range of nm.

Reference numeral 6 denotes a cathode which is usually in close contact with the electron injecting / transporting layer 5 and has a work function lower than that of the compound used in the electron injecting / transporting layer 5 (usually 5 eV or less), for example, lithium, magnesium, It is formed by vapor deposition of a metal or metal oxide such as calcium, sodium, lithium, silver, copper, aluminum and indium, or a conductive compound alone or in combination. The thickness of the cathode 6 is not particularly limited, and is usually 10 nm or more so that the resistivity is 1 kΩ / □ or less, while taking into account the conductivity, the manufacturing cost, the thickness of the entire element, light transmittance, and the like.
Preferably, it is set to 50 to 500 nm. In addition,
If necessary, for example, an aromatic diamine compound, a quinacridone compound, a naphthacene compound, an organosilicon compound, or an organic compound, in order to enhance adhesion between the cathode 6 and the electron injection / transport layer 5 containing an organic compound. An interface layer containing a phosphorus compound may be provided. The electron cathode 6
In order to facilitate the transfer from the electron injection / transport layer 5 to the electron injection / transport layer 5, in the same manner as in the anode 2, an alkali such as lithium fluoride, lithium oxide, etc. A thin film having a thickness of 0.1 to 2 nm may be formed using a metal compound or an alkaline earth metal compound.

As described above, the organic EL device of the present invention
An anode 2, a light-emitting layer 4, a cathode 6, and, if necessary, a hole injection / transport layer 3, an electron injection / transport layer 5, and / or a hole blocking layer are adhered to an adjacent layer on the substrate 1 with an adjacent layer. It can be obtained by integrally forming while making. In forming each layer, in order to minimize oxidation and decomposition of organic compounds, and adsorption of oxygen and moisture, etc.,
It is desirable to work partly under a high vacuum, specifically at 10 ^-5 Torr or less. In forming the light emitting layer,
The mixing ratio of the host compound and the guest compound is adjusted in advance by mixing the host compound and the guest compound at a predetermined ratio, or by controlling the heating rates of the two in vacuum deposition independently of each other. The organic EL device thus constructed is partially or entirely sealed with, for example, a sealing glass or a metal cap under an inert gas atmosphere, in order to minimize deterioration in the use environment, or It is desirable to cover with a protective layer made of UV curable resin.

The method of using the organic EL device according to the present invention will be described. The organic EL device according to the present invention can be applied with a relatively high voltage pulse voltage intermittently or a relatively low voltage depending on the application. Driving is performed by continuously applying a non-pulse voltage (usually 3 to 50 V). The organic EL device of the present invention emits light only when the potential of the anode is higher than the potential of the cathode. Therefore, the organic E of the present invention
The voltage applied to the L element may be direct current or alternating current, and the waveform and period of the applied voltage may be appropriate. When an alternating current is applied, the organic EL device of the present invention:
In principle, the luminance repeatedly increases and decreases or blinks repeatedly according to the waveform and cycle of the applied alternating current. In the case of the organic EL device shown in FIG. 1, when a voltage is applied between the anode 2 and the cathode 6, the anode 2
From the cathode 6 reach the light emitting layer 4 via the hole injecting / transporting layer 3, and electrons injected from the cathode 6 reach the light emitting layer 4 via the electron injecting / transporting layer 5. as a result,
In the light emitting layer 4, recombination of holes and electrons takes place, and the resulting coumarin derivative in the excited state emits desired light through the anode 2 and the substrate 1. The organic EL device of the present invention usually has a green to red range, particularly 500 to 6, though it depends on the structure and the mixing ratio of the coumarin derivative and the host compound used in combination.
It has a light emission maximum such as a fluorescence maximum near 50 nm. The light emission is usually such that x is in the range of 0.33 to 0.63 and y is 0.36 to 0.63 on the xy chromaticity diagram.
In the range.

The organic EL device of the present invention has excellent durability and high luminous efficiency, and as a result, has high luminance. Therefore, the organic EL device can be used in a variety of light emitting devices and information display devices for visually displaying information. Has a variety of uses. Since the luminous body using the organic EL element of the present invention as a light source has low power consumption and can be formed in a lightweight panel shape,
In addition to light sources for general illumination, for example, liquid crystal elements, copying machines, printing devices, electrophotographic devices, computers and their applied equipment, industrial control equipment, electronic measuring instruments, analytical instruments, general instruments, communication equipment, medical electronic measurement It is useful as an energy-saving and space-saving light source for equipment, equipment mounted on vehicles including automobiles, ships, aircraft, spaceships, etc., aircraft control equipment, interiors, signs, signs, and the like. When the organic EL device of the present invention is used for an information display device such as a computer, a television, a video, a game, a clock, a telephone, a car navigation, an oscilloscope, a radar, and a sonar, the organic EL device may be used alone or in blue. E emitting in the green, green and / or red regions
The driving is performed by applying a general-purpose simple matrix system or an active matrix system as needed while combining with the L element.

Furthermore, as described above, the coumarin derivative of the present invention has an absorption maximum in the visible region and substantially absorbs visible light, and is thus polymerized by exposing the polymerizable compound to visible light. For sensitizing a solar cell, a chromaticity adjusting material for an optical filter, and a material for dyeing various kinds of clothing. In particular, most of the coumarin derivatives of the present invention have an absorption maximum wavelength, for example, a gas laser such as an argon ion laser or a krypton ion laser, a semiconductor laser such as a CdS laser, a distributed feedback type or a distributed Bragg reflection type Cd-YA.
As it is close to the oscillation line (wavelength 400 to 550 nm) of general-purpose lasers such as solid-state lasers such as G lasers, it is compounded as a photosensitizer in a photopolymerizable composition using such a laser as an exposure light source. By doing so, it can be used very advantageously in the fields of information recording such as facsimile, copier, printer, etc., in the field of printing such as flexo plate making and gravure plate making, and in the field of printed circuit such as photoresist.

When the coumarin derivative of the present invention is used as a laser active substance, it is purified in the same manner as in the case of constituting a known dye laser oscillator, and dissolved in a solvent as appropriate.
If necessary, after adjusting the pH of the solution to an appropriate level,
It is sealed in a dye cell in a laser oscillation device. The coumarin derivative of the present invention is characterized by not only obtaining an amplification gain in an extremely wide wavelength range in the visible region, but also having high light resistance and hardly deteriorating even when used for a long time, as compared with known analogous compounds.

The coumarin derivative of the present invention may be used together with one or more other materials that absorb light in the ultraviolet region and / or the visible region, if necessary, together with general clothing or other than clothing, such as drapes. , Lace, casement, print, venetian blind, roll screen, shutter, goodwill, blanket, futon, futon, futon cover, futon cotton, sheets, cushion, pillow, pillowcase, cushion, mat, carpet, sleeping bag, tent , Interior materials of vehicles including automobiles, window glazing, window glazing, etc.
Health supplies such as disposable diapers, diaper covers, eyeglasses, monocles, lownets, shoe insoles, shoe linings, luggage, furoshiki, umbrellas, parasols, stuffed animals, lighting equipment, and, for example, CRT displays, electroluminescence display,
Optical filters, panels, and screens for information display devices such as television receivers and personal computers using plasma displays, etc., sunglasses, sunroofs, PET bottles, storages, plastic houses, refrigerators, optical fibers, prepaid cards, microwave ovens , Viewing windows such as ovens, and further, packaging materials for packing, filling or storing these articles, filling materials,
When used for containers, etc., it can not only prevent or reduce obstacles and inconveniences caused by environmental light such as natural light and artificial light in living things and goods, but also adjust the color, color tone, texture, etc. of goods and reflect light from goods. There is a benefit in that the light that passes or is transmitted can be adjusted to a desired color balance.

Hereinafter, embodiments of the present invention will be described based on examples.

[0075]

Example 1 <Coumarin derivative> 10 ml of N, N-dimethylformamide was placed in a reaction vessel, and 3.4 g of the compound represented by the chemical formula 28 and the compound 1.
After adding 8 g, the mixture was heated under reflux for 4 hours. The reaction mixture was cooled to ambient temperature, and the precipitated crystals were collected by filtration, purified by silica gel column chromatography using chloroform as a developing solvent, and then recrystallized with a mixed solution of chloroform / methanol to give a coumarin derivative represented by the chemical formula 2. 1.1 g of orange crystals were obtained.

[0076]

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[0077]

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A portion of the crystal was taken, and the visible absorption spectrum and the fluorescence spectrum in a methylene chloride solution were measured according to a conventional method. As a result, an absorption maximum and a fluorescence maximum were observed at wavelengths of 450 nm and 515 nm, respectively. Further, according to a conventional method, ¹ % of chloroform-d solution was used.
When an H-nuclear magnetic resonance spectrum (hereinafter abbreviated as “ ¹ H-NMR spectrum”) was measured, the chemical shift (δ, TMS) was 1.35 (6H, s), 1.61 (6).
H, s), 1.79 (2H, t), 1.84 (2H,
t), 2.95 (3H, s), 3.27 (2H, t),
3.35 (2H, t), 7.50 (1H, s), 7.5
3 (1H, t), 7.60 (1H, t), 7.85 (1
H, d), 7.96 (1H, d), 8.09 (1H,
Peaks were observed at d) and 8.14 (1H, d).

Further, when a commercially available DSC analyzer (trade name “DSC220U”, manufactured by Seiko Instruments Inc.) was used for DSC analysis at a rate of temperature increase of 10 ° C./min, the glass transition point of the coumarin derivative of this example was found to be 10
9 ° C. Separately, the analogous compound prepared by a general-purpose method and represented by the chemical formula 30 in which the 4-position of the coumarin skeleton in the chemical formula 2 is a hydrogen atom, was similarly subjected to DSC.
Analysis showed that the glass transition point was 133 ° C.

[0080]

Embedded image

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in a violet region and a green region, respectively, is a light absorber,
Photochemical polymerization, solar cell, dyeing, organic EL as luminescent agent
It is useful in various fields including elements, optical filters, and dye lasers.

[0082]

Example 2 <Coumarin derivative> 10 ml of N, N-dimethylformamide was placed in a reaction vessel, and 3.0 g of the compound represented by the chemical formula 31 and 3.0 g of the compound represented by the chemical formula 29 were prepared.
After adding 4 g, the mixture was heated under reflux for 4 hours. The reaction mixture was cooled to ambient temperature, and the precipitated crystals were collected by filtration, purified by silica gel column chromatography using chloroform as a developing solvent, and then recrystallized with a mixed solution of chloroform / methanol to give a coumarin derivative represented by Chemical Formula 8 0.8 g of red crystal was obtained.

[0083]

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A portion of the crystal was taken, and the visible absorption spectrum and the fluorescence spectrum in a methylene chloride solution were measured according to a conventional method. As a result, an absorption maximum and a fluorescence maximum were observed at wavelengths of 462 nm and 653 nm, respectively. Further, according to a conventional method, ¹ % of chloroform-d solution was used.
When the H-NMR spectrum was measured, the chemical shifts (δ, TMS) were 1.32 (6H, s) and 1.56 (6
H, s), 1.78 (2H, t), 1.84 (2H,
t), 3.30 (2H, t), 3.38 (2H, t),
7.49 (1H, s), 7.52 to 7.64 (2H,
m), 7.88 (1H, d), 7.97 (1H, d),
Peaks were observed at the positions of 8.04 (1H, d) and 8.11 (1H, d). Further, the DSC analysis performed in the same manner as in Example 1 showed that the coumarin derivative of this example had a glass transition point of 100 ° C.

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the violet region and the red region, respectively, is a light absorber,
It is useful as a luminescent agent in various fields such as photochemical polymerization, solar cells, dyeing, optical filters, organic EL devices, and dye lasers.

[0086]

Example 3 <Coumarin derivative> 5 ml of N, N-dimethylformamide was placed in a reaction vessel, and 2.0 g of the compound represented by the chemical formula 32 and 1.3 g of the compound represented by the chemical formula 29 were obtained.
After adding g, the mixture was heated under reflux for 4 hours. The reaction mixture was cooled to ambient temperature, and the precipitated crystals were collected by filtration, purified by silica gel column chromatography using chloroform as a developing solvent, and then recrystallized with a mixed solution of chloroform / methanol to give a coumarin derivative represented by the formula (15). 1.0 g of orange crystals were obtained.

[0087]

Embedded image

A portion of the crystal was taken, and the visible absorption spectrum and the fluorescence spectrum in a methylene chloride solution were measured according to a conventional method. As a result, an absorption maximum and a fluorescence maximum were observed at wavelengths of 450 nm and 509 nm, respectively. Further, according to a conventional method, ¹ % of chloroform-d solution was used.
When the H-NMR spectrum was measured, the chemical shift (δ, TMS) was 1.36 (6H, s), 1.45 (3
H, t), 1.61 (6H, s), 1.78 to 1.8
6 (4H, m), 3.27 (2H, t), 3.35 (2
H, t), 3.44 (2H, q), 7.52 (1H,
s), 7.56 (1H, t), 7.60 (1H, t),
7.85 (1H, d), 7.96 (1H, d), 8.0
Peaks were observed at 8 (1H, d) and 8.14 (1H, d).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in a violet region and a green region, respectively, is a light absorber,
It is useful as a luminescent agent in various fields such as photochemical polymerization, solar cells, dyeing, optical filters, organic EL devices, and dye lasers.

[0090]

Embodiment 4 <Coumarin derivative> Embodiments 1 to 3
The coumarin derivative obtained by any one of the above methods was charged into a water-cooled sublimation purification apparatus, and purified by sublimation by heating under reduced pressure according to a conventional method.

The coumarin derivative of this example having a high purity is extremely useful in the field of organic electronics such as organic EL devices and dye lasers.

The coumarin derivative according to the present invention comprises:
Although there are some differences in the charging conditions and yields depending on the structure, for example, the methods of Examples 1 to 4 including those represented by Chemical Formulas 1 to 27 other than those described above, The desired amount can be prepared according to the method.

[0093]

Embodiment 5 <Organic EL Device> A stacked organic EL device having the structure shown in FIG. 1 using the coumarin derivative according to the present invention.
An element was manufactured.

A glass substrate 1 having a transparent ITO electrode with a thickness of 150 nm as an anode 2 patterned with a water vapor is ultrasonically cleaned using a detergent, pure water, acetone and ethanol, dried, and irradiated with ultraviolet ozone. After the treatment, the pressure was fixed to a vacuum evaporation apparatus, and the pressure was reduced to 8 × 10 ⁻⁷ Torr. Next, a tetramer of triphenylamine represented by Formula 33 was deposited on the surface of the glass substrate 1 having the ITO electrode to a thickness of 60 nm to form the hole injection / transport layer 2. Thereafter, while monitoring with a film thickness sensor, the coumarin derivative of the present invention represented by Chemical Formula 2 and tris (8-quinolinolate) aluminum were used as a guest luminescent agent and a host luminescent agent, respectively, in a weight ratio of 1:
A light emitting layer 4 is formed by co-evaporation to a thickness of 20 nm at 100, and an electron injection / transport layer 5 is formed by depositing tris (8-quinolinolato) aluminum to a thickness of 40 nm. Was deposited in this order to a thickness of 0.5 nm and 160 nm, respectively, to form a cathode 6. Thereafter, under a nitrogen atmosphere, the entire device was sealed with a glass plate and an ultraviolet curable resin to obtain an organic EL device for green light emission.

[0095]

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The organic EL device thus obtained is usually
According to the method, while measuring the emission spectrum,
At an ambient temperature of 85 ° C., the initial emission luminance is 2,400 cd.
/ M ^TwoInvestigate the change over time in luminance when driving at constant current with
Life expectancy was estimated. Separately, coumarin induction represented by Chemical Formula 2
An analogous compound represented by Formula 30 is used instead of the conductor.
A control system was prepared and treated as described above to serve as a control.

According to the emission spectrum, the organic EL of this example
The device has an emission maximum in a green region having a wavelength of 528 nm, and xy
As for the color coordinates of light emission in the chromaticity diagram, x was 0.34 and y was 8.61. Light emission is at an ambient temperature of 80 ° C.
Even if the device was driven at a constant current at an initial luminance of 2,400 cd / m ² , it stably continued, and the life under such conditions (the driving time during which the initial luminance was reduced by half) was estimated to be about 65 hours. On the other hand, although the control organic EL element had relatively good color purity, the life when driven at a constant current under the same conditions as described above was about 25 hours, which was compared with the organic EL element according to the present invention. Was significantly shorter. The compound represented by Formula 30 is
It is a substance having particularly high durability among analogous compounds and exhibiting durability comparable to N, N'-dimethylquinacridone which has already been practically used as a material for a light emitting layer in an organic EL device. Furthermore, when the current efficiency and the external quantum efficiency at 300 cd / m ^2, which is the practical luminance, were measured according to a conventional method, the current efficiency and the external quantum efficiency of the organic EL device of this example were 11.6 cd / A, respectively.
And 3.2%, the current efficiency and the external quantum efficiency of the organic EL device manufactured in the same manner as above using N, N′-dimethylquinacudrine instead of the coumarin derivative according to the present invention are as follows. And 1.9 cd / A and 1.8%, respectively, which were significantly inferior to the organic EL device of this example. These facts indicate that the organic EL according to the present invention
That the element is useful as a green light emitting element,
It shows that by using the coumarin derivative of the present invention, an organic EL device having a long life and a high luminance and a high efficiency that can endure a severe use environment can be realized.

[0098]

Embodiment 6 <Organic EL Device> An organic EL device for emitting light in the same manner as in Embodiment 5 except that a coumarin derivative represented by Chemical Formula 8 was used instead of the coumarin derivative represented by Chemical Formula 2. Was prepared.

The organic EL device of this example had a light emission maximum in the red region at a wavelength of 614 nm, and the color coordinates of light emission in the xy chromaticity diagram were such that x was 0.52 and y was 0.45. Further, according to a conventional method, a practical luminance of 300 cd / m
^2, the current efficiency and the external quantum efficiency of the organic EL device of this example were 3.4 cd / A and 1.7%, respectively. Instead of the coumarin derivative, 4- (dicyanomethylene) -2-tert-butyl-6- (1,1, which has already been put to practical use as a light emitting layer material.
7,7-tetramethyluroridyl-9-enyl) -4H
The current efficiency and the external quantum efficiency of the organic EL device manufactured in the same manner as described above using pyran were 1.7c, respectively.
d / A and 1.3%, which were significantly inferior to the organic EL device of this example. This fact indicates that the organic EL device according to the present invention is useful as a high-luminance, high-efficiency red light-emitting device.

[0100]

Embodiment 7 <Display Panel> FIG.
This is an example of a simple matrix type display panel (20 electrode rows in the horizontal direction and 30 electrode rows in the vertical direction) mainly comprising the organic EL element of the present invention. Such a display panel can be manufactured as follows. it can.

That is, first, ITO was applied to one side of the glass substrate 10 in accordance with the method of the fifth or sixth embodiment.
After forming the anode 14 using a transparent electrode, the anode 14 is processed into a stripe shape by a wet etching method. Then
The hole injecting / transporting layer 16 and the light emitting layer 18 are sequentially formed according to the method of the fifth embodiment, and the cathode 20 is formed using a mechanical mask.
After forming in a stripe shape, a glass plate (not shown)
And the organic EL element is sealed with an ultraviolet curable resin. In the display panel of this example, a heat radiating plate or a cooling fan may be mounted on the back side of the cathode 20 as needed in order to suppress a rise in temperature during use.

[0102]

Embodiment 8 <Information Display Apparatus> FIG. 3 shows an example of an information display apparatus using a display panel manufactured by the method of Embodiment 7. In FIG. 3, reference numeral 30 denotes an output voltage of 4.5.
V DC power supply, and its output terminal has two booster circuits 3
2, 34 are connected. The booster circuit 32 has 5 to 12
A DC power in the range of V can be supplied, and its output terminal is connected to the driver circuit 36. The other booster circuit 34 supplies a constant voltage of 5 V to the microcomputer 3
8.

The microcomputer 38 includes an I / O interface 38a for exchanging signals with the outside, a ROM 38b for recording programs and the like, a RAM 38c for recording various data, and a CP for executing various operations.
U38d. The microcomputer 38 is connected to a clock generation circuit 40 for supplying a clock signal of 8 MHz to the microcomputer 38 and two oscillation circuits 42 and 44. The two oscillation circuits 42 and 44 are connected to the microcomputer 38. To
Each is for supplying a signal of 5 to 50 Hz for controlling the display speed and a signal of 0.2 to 2 kHz for controlling the scanning frequency.

Reference numeral 48 denotes a display panel mainly comprising the organic EL element of the present invention, which is connected to the microcomputer 38 via driver circuits 36 and 46. The driver circuit 36 is a circuit that controls the application of the DC voltage from the booster circuit 32 to the display panel, and includes one of a plurality of transistors individually connected to a vertical electrode row in the display panel 48. When turned on, the booster circuit 32 is connected to the vertical electrode row connected to the transistor.
Will be applied. On the other hand, the driver circuit 46 includes a plurality of transistors individually connected to a horizontal electrode row of the display panel 48. Therefore, when one of the transistors in the driver circuit 36 is turned on, the voltage from the booster circuit 32 is applied to the vertical electrode row connected to the transistor. On the other hand, the driver circuit 46 includes a plurality of transistors individually connected to a horizontal electrode row of the display panel 48. When any of the transistors in the driver circuit 46 is turned on, the horizontal circuit connected to the transistor is turned off. The electrode rows in the directions are grounded.

Since the information display device of this embodiment is configured as described above, when the transistors in the driver circuits 36 and 46 are turned on in accordance with the instruction of the microcomputer 38, the gap between the corresponding electrode rows in the vertical and horizontal directions of the display panel 48 is obtained. Is applied, and the organic EL element located at the intersection thereof emits light. Therefore, for example, one horizontal electrode row is selected by appropriately controlling the driver circuit 46, and the electrode row is connected to the vertical electrode row by appropriately controlling the driver circuit 36 while grounding the electrode row. When the transistors are sequentially turned on, the entire selected horizontal electrode row is scanned in the horizontal direction, and a given pixel is displayed. By repeating such scanning sequentially in the vertical direction, an entire screen can be displayed. Note that the driver circuit 3 in this example is
6 has a data register for one row of electrodes,
It is preferable to drive the transistor based on the recorded data.

The information to be displayed may be supplied from the outside in accordance with the display speed and cycle, or the information having a certain pattern such as character information may be stored in the ROM 38b in advance. In advance, this may be used as data. Also, normal NT
When displaying a television broadcast by the SC system,
First, a received signal is separated into a horizontal synchronizing signal and a vertical synchronizing signal according to a horizontal frequency and a vertical frequency based on a broadcast standard, and a video signal is converted into a digital signal corresponding to the number of pixels of the display panel 48. By appropriately synchronizing and supplying these signals to the microcomputer 38, a television broadcast can be displayed on the display panel 48.

[0107]

As described above, the coumarin derivative of the present invention has a property of having an absorption maximum in the visible region and substantially absorbing visible light, and having a light emission maximum in the visible region and, when excited, Since it also has the property of emitting visible light, it requires an organic compound having such properties as a light absorbing agent and a luminescent agent. For example, photochemical polymerization, solar cells, dyeing, optical filters, and organic EL It is useful in various fields including devices and dye lasers.

In particular, it has an emission maximum in the visible region, and
The coumarin derivative of the present invention having a glass transition point in the range of 100 to 110 ° C. emits a visible light having a relatively long wavelength, particularly, a green light to a red light in an organic EL device. Is stable for a long time. The organic EL device according to the present invention has high luminous efficiency,
As a result, since the luminance is large, by appropriately configuring the panel shape or the like, a luminous body in general lighting as a light source that emits visible light, and information such as image information and character information are visually displayed. It can be used very advantageously in a wide variety of information display devices.

Such a coumarin derivative comprises a coumarin compound having an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions of the coumarin skeleton, respectively, and having a urolidine skeleton at a site other than the 3- and 4-positions. A desired amount can be obtained by the production method of the present invention via a step of reacting a hydrocarbon having a thiol group and a primary amino group bonded to adjacent carbon atoms.

The present invention having such remarkable functions and effects can be said to be a significant invention which greatly contributes to the art.

[Brief description of the drawings]

FIG. 1 is a schematic view of an organic EL device according to the present invention.

FIG. 2 is a schematic diagram of a display panel according to the present invention.

FIG. 3 is a block diagram of an information display device according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 10 Substrate 2, 14 Anode 3, 16 Hole injection / transport layer 4, 18 Emission layer 5 Electron injection / transport layer 6, 20 Anode 30 DC power supply 32, 34 Boost circuit 36, 46 Driver circuit 38 Microcomputer 40 Clock Generation circuit 42, 44 Oscillation circuit 48 Display panel

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05B 33/22 H05B 33/22 BD (72) Inventor Natsuko Ishida 1-2-3 Shimoishii, Okayama City, Okayama Prefecture Stock Inside the Hayashibara Biochemical Laboratory (72) Inventor Chika Sasaki 1-2-3 Shimoishii, Okayama City, Okayama Prefecture Inside the Hayashibara Biochemical Laboratory Company (72) Inventor Sadaharu Suga 1-2-3 Shimoishii, Okayama City, Okayama Prefecture No. 1 in the Hayashibara Institute of Biochemical Research Co., Ltd. (72) Kuki Fujikawa, inventor 41 at Chukuji-Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside the Toyota Central R & D Laboratories Co., Ltd. 41-1 Toyota Central Research Laboratory Co., Ltd. (72) Inventor Yasukun Taga Nagamute-cho, Aichi-gun Aichi-gun Nagakute-cho Chuchi-jimichi 41-1 F-term in Toyota Central Research Laboratory Co., Ltd. 3K007 AB02 AB03 AB04 AB11 BA06 BB01 CA01 CB01 DA01 DB03 EB00 4C050 AA02 BB07 CC07 DD08 EE02 FF02 FF04 FF05 GG03 HH03 HH04 5C094 AA08 AA10 AA31 BA12 BA27 CA19 CA24 DA13 EA04 EA05 EB02 FB01

Claims (20)

[Claims] 1. A coumarin derivative having a hydrocarbon group bonded to the 4-position of a coumarin skeleton and having a urolidine skeleton and a benzothiazole skeleton at a position other than the 4-position. 2. The coumarin derivative according to claim 1, which has an absorption maximum in a visible region. 3. The coumarin derivative according to claim 1, which has a light emission maximum in a visible region. 4. The coumarin derivative according to claim 1, wherein the glass transition point is in the range of 100 to 110 ° C. 5. The coumarin derivative according to claim 1, wherein the coumarin derivative is represented by the general formula 1. Embedded image In the general formula 1, R ₁ represents a hydrocarbon group, and the hydrocarbon group may have a substituent. R _{2 to} R ₅ each independently represent a hydrogen atom or an aliphatic hydrocarbon group.
Z represents an aromatic ring fused to a thiazole ring. 6. A coumarin derivative having an emission maximum in a visible region and having a glass transition point of 100 to 110 ° C. 7. A light absorber comprising the coumarin derivative according to any one of claims 1 to 6. 8. The light absorber according to claim 7, which is used as a photosensitizer. 9. A luminescent agent comprising the coumarin derivative according to claim 1. 10. The luminescent agent according to claim 9, which is used as a material for a luminescent layer in an organic electroluminescent device. 11. The luminescent agent according to claim 9, which is used as a laser-active substance. 12. An organic electroluminescent device using the coumarin derivative according to claim 1. 13. A structure in which a hole injection / transport layer, an electron injection / transport layer and / or a hole block layer are provided, if necessary, together with an anode, a light-emitting layer and a cathode. An organic electroluminescent device according to claim 12, comprising the coumarin derivative according to any one of claims 1 to 6. 14. The organic electroluminescent device according to claim 12, wherein a coumarin derivative is used in combination with another luminescent compound. 15. The organic electroluminescent device according to claim 12, which comprises a quinolinol metal complex together with the coumarin derivative according to any one of claims 1 to 6. 16. The organic electroluminescent device according to claim 12, which emits visible light in a green range or a red range. 17. A display panel using the organic electroluminescent device according to claim 12. 18. An information display device using the organic electroluminescent device according to claim 12. 19. A coumarin compound having an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions in the coumarin skeleton, respectively, and having a urolidine skeleton at a site other than the 3- and 4-positions, and an adjacent carbon atom. The method for producing a coumarin derivative according to any one of claims 1 to 6, further comprising a step of reacting an aromatic hydrocarbon formed by bonding a thiol group and a primary amino group to an atom. 20. A step of reacting a compound represented by the general formula 2 having R _{1 to} R ₅ corresponding to the general formula 1 with a compound represented by the general formula 3 having Z corresponding to the general formula 1. 20. The method for producing a coumarin derivative according to claim 19, wherein Embedded image Embedded image