WO2001090098A1

WO2001090098A1 - Koumarin derivative and use thereof

Info

Publication number: WO2001090098A1
Application number: PCT/JP2001/004219
Authority: WO
Inventors: Makoto Satsuki; Yoshimi Takahashi; Chika Sasaki; Akira Shinpo; Sadaharu Suga; Hisayoshi Fujikawa; Atsushi Miura; Shizuo Tokito; Yasunori Taga
Original assignee: Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo
Priority date: 2000-05-24
Filing date: 2001-05-21
Publication date: 2001-11-29

Abstract

A specific coumarin derivative having a chalcone-like structure in the molecule thereof; a luminescent material for an organic electroluminescence element which comprises the specific coumarin derivative and an organic electroluminescence element comprising the luminescent material; and an information display device using the organic electroluminescence element. The specific coumarin derivative has the maximum luminescence in a red region or a near-infrared region.

Description

Description Coumarin derivatives and their uses Technical field

The present invention relates to a coumarin derivative and its use, and more particularly, to a luminescent agent for an organic electroluminescent device. Background art

In the field of information display, electroluminescent devices have been spotlighted as next-generation display devices. At present, CRTs are mainly used for relatively large information display devices such as computer terminals and television receivers. However, CRTs are both large in volume and weight and have high operating voltages, making them unsuitable for consumer devices and small devices that emphasize portability. Small devices need to be thinner, lighter, flat, have lower operating voltage, and consume less power. At present, liquid crystal devices are used in many fields because of their low operating voltage and relatively low power consumption. However, since the contrast of an information display device using a liquid crystal element changes depending on the viewing angle, a clear display cannot be obtained unless the image is read within a certain angle range, and a backlight is usually required. However, there is a problem that power consumption does not become so small. An organic EL device has emerged as a display device that solves these problems.

Organic EL devices usually have a light-emitting layer containing a light-emitting compound interposed between an anode and a cathode, and apply a DC voltage between the anode and the cathode to apply holes and electrons to the light-emitting layer. Are injected into each other, and they are recombined with each other to create an excited state of the luminescent compound. This is a light-emitting element that uses light emission such as fluorescence or phosphorescence emitted when returning to the device. The organic EL device is capable of emitting light by forming a light emitting layer by selecting an appropriate organic compound as a host compound and changing a guest compound (dopant) to be combined with the host compound. There is a feature that the color tone can be changed appropriately. Further, depending on the combination of the host compound and the guest compound, there is a possibility that the luminance and the lifetime of light emission can be significantly improved. In the first place, an organic EL element emits light by itself, so an information display device using it does not depend on the viewing angle and does not require a backlight. It is said to be an element.

However, in organic EL devices that emit light in the green range, improvements in luminous efficiency and emission spectrum by the addition of a guest compound have been reported, but organic EL devices that emit light in the red range have not been reported. However, since an effective guest compound has not yet been found, not only the color purity and luminance but also the durability and the reliability are still insufficient. For example, the organic EL device disclosed in Japanese Patent Application Laid-Open No. 10-60427 and US Pat. No. 4,769,922 has a low luminance and a pure red light emission. Because of this, there is still a problem in achieving full color.

In view of such a situation, an object of the present invention is to provide an organic compound useful in various fields, such as an organic EL device, in which a compound having a light emission maximum in a visible region is required. Disclosure of the invention

In order to solve these problems, the present inventors have conducted intensive research and searched. As a result, a chalcone-like structure (1,3—dipyronyl-2-propene) was found in the molecule. ) (Hereinafter sometimes simply referred to as “coumarin derivative”) has a light emission maximum in a target visible region, and when used in an organic EL device as a luminescent agent, It has been found that high-luminance red to orange light is emitted over a long period of time. The present invention is based on the discovery of the industrially useful properties of certain coumarin derivatives. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram 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 the information display device according to the present invention. In the figure, 1 and 10 are substrates, 2, and 14 are anodes, 3, 16 are hole injection and transport layers, 4, 18 are light emitting layers, 5 is electron injection and transport layers, 6 , 20 is the cathode, 30 is the DC power supply, 32, 34 is the booster circuit, 36, 46 is the driver circuit, 38 is the microcomputer, 40 is the clock generation circuit, 42 and 44 indicate an oscillation circuit, and 48 indicates a display panel. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention solves the above-mentioned problems by providing a coumarin derivative having a chalcone-like structure in a molecule, and in particular, by providing a luminescent agent for an organic EL device comprising a coumarin derivative represented by the general formula 1. Is what you do.

In the general formula 1, R 1 to R ₂ represent a hydrogen atom or an appropriate substituent. Examples of the individual substituent include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, a 1-propyl group, a 2-propyl group, an isopropyl group, and a butyl group. , Isoptyl, sec-butyl, tert-butyl, 2-butenyl, Ί, 3-butadienyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl Group, 2-pentenyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, aliphatic hydrocarbon group such as octyl group, cyclopropyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Alicyclic hydrocarbon groups such as xyl group, cyclohexylmethyl group, dicyclohexenyl group, phenyl group, 0-tolyl group, m-tolyl group, and P-tolyl group Aromatic groups such as Ryl, 0-cumenyl, m-cumenyl, p-cumenyl, xylyl, mesityl, biphenylyl, styryl, cinnamoyl, naphthyl, anthenyl, and phenanthryl Complex such as group hydrocarbon group, furyl group, phenyl group, pyrrolyl group, pyrrolidinyl group, pyridyl group, piperidinyl group, piperidyl group, piperazinyl group, morphonyl group, quinolyl group, and isoquinolyl group Ether groups such as ring groups, methoxy groups, ethoxy groups, trimethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, tert-butoxy groups, and phenoxy groups, and methoxycarbonyl groups And alkoxycarbonyl groups such as ethoxycarbonyl group, halogen groups such as chloro group, chloro group, promo group and iodo group, amino Amino groups such as methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, butylamino group, dibutylamino group, pentylamino group, cyclohexylamino group, and the like; Electron-withdrawing groups such as a group, an acyl group, a sulfo group, a sulfino group, a cyano group, and a nitro group. You. In these substituents, one or more of the hydrogen atoms are, for example, methyl, ethyl, propyl, isopropyl, butyl, isopropyl, sec-butyl, tert-butyl, pentyl Group, isopentyl group, neopentyl group, tert-pentyl group and other short-chain long-chain aliphatic hydrocarbon groups, methoxy group, trihalomethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group Alkoxy groups such as tert-butoxy group, methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, etc., methylsulfonyl group, trimethylfluoromethylsulfonyl group, ethyl Alkylsulfonyl groups such as sulfonyl groups, halo such as chloro groups, chloro groups, promo groups and iodo groups It may be substituted by a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a sulfino group, or the like.

As described above, the coumarin derivative referred to in the present invention is a coumarin derivative having a chalcone-like structure in the molecule, particularly a compound having a basic skeleton represented by the general formula 1, and As long as the compound can be used alone or in combination with another light-emitting compound as a light-emitting agent for an organic EL device, R _{1 to} R 12 in the general formula 1 are hydrogen atoms or an appropriate substituent. It does not matter. The desirable group of coumarin derivatives used in the present invention depends on the type and amount of the host compound, the material for the hole injection / transport layer, the material for the electron injection Z transport layer, etc., which are used in combination in the organic EL device. for example, R ₂ and / or R "in the general formula Ί is a substituent represented by the general formula 2, in its R ₂ and or R _n, is R u and Roh or R _{1 4} in the general formula 2, A carbon atom adjacent to the carbon atom to which R ₂ is bonded, or a carbon atom adjacent to the carbon atom to which R is bonded to form a cyclic structure Z, Z ₂ , Z 3 and Z or Z ₄ And those represented by general formulas 3 to 5. -General formula 2:

In the general formula 2, R ₁₃ and R each independently represent a hydrogen atom or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an ether group, and these aliphatic hydrocarbon groups, aromatic hydrocarbon groups And the ether group may have a substituent. As the aliphatic hydrocarbon group, aromatic hydrocarbon group and ether group in the general formula 2, and the substituents which they may have, the same groups as those in R 1 to R ₁₂ in the general formula 1 are selected. Therefore, the cyclic structures Z and Z ₄ are each a monocyclic or polycyclic five-membered heterocyclic group containing one or more nitrogen atoms in the ring and having one or more substituents. It is a ring or a six-membered heterocyclic ring. When any of the cyclic structures Z 1 to Z ₄ exists, R ₁ , R ₃ , and R _{1 (1} or R ₂ in the general formula 1) are apparently absent. Specific examples of the coumarin derivative used in the present invention include, for example, those represented by Chemical Formulas 1 to 62. Each of these compounds has a light emission maximum such as a fluorescence maximum in a red or near red region and forms a stable thin film in a glassy state. Therefore, these may be used alone or in combination with another light emitting compound. Accordingly, it can be used very advantageously as a luminescent agent for an organic EL device.

Chemical formula 1:

Chemical formula 2:

Chemical formula 3:

C2H5 Formula 5:

Formula 6:

Formula 7:

Formula 11:

Formula 12:

Chemical formula 13:

Chemical formula :

Chemical formula 16:

Chemical formula 17:

Chemical formula 18:

Chemical formula 19:

Formula 20:

Chemical formula 21

Formula 23:

Chemistry

Formula 25:

Chemical formula 27:

Chemistry

Chemical formula 29:

Chemical formula 31:

Formula 32:

ヽ Ό Ο 、, 0 Chemical formula 36:

Chemical formula 40:

Chemical formula 41:

Chemical formula 42:

Formula 44:

Chemical formula 45:

Chemical formula 46:

Chemical formula 47:

Formula 4B:

Chemical Formula 49:

Formula 50:

Chemical Formula 51

Chemical Formula 52:

Chemical Formula 53:

Chemical formula 54:

Chemical formula 56:

OH O 3 H ₃ C,, CH

Chemical formula 59

Chemical formula 62

The coumarin derivative used in the present invention can be prepared by various methods, but if importance is placed on economy, for example, it is represented by the general formula 6 having R, to R ₆ corresponding to the general formula 1. A preferred method is to react a compound represented by the general formula 7 having R ₈ to R ₂ corresponding to the general formula 1 with a compound represented by the general formula 7.

—General formula 6

General formula 7:

That is, the compound represented by the general formula 6 and the compound represented by the general formula 7 are respectively dissolved in a reaction vessel in an appropriate amount (usually equimolar) and, if necessary, appropriately in a solvent. Lithium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium acetate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, anily Basic compounds such as N, N-dimethylaniline, N, N-Jetylaniline, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid Add acidic compounds such as acid and acetic anhydride, and Lewis acidic compounds such as aluminum chloride, zinc chloride, tin tetrachloride and titanium tetrachloride, and then heat to reflux. Heating and with stirring is reacted at a temperature above et ambient temperature or ambient temperature.

Examples of the solvent include pentane, hexane, cyclohexane, hydrocarbons such as hexane, benzene, toluene, and xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, and the like. Trichloroethylene, tetrachloroethylene, cyclobenzene, promobenzene, α-halogen compounds such as cyclobenzene, 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 glycol Alcohols and phenols such as glycerol and glycerin, getyl ether, diisopropyl ether, tetrahydrofuran, tetrahydroviran, 1,4-dioxane, anisol, 1,2-dimethyloxetane, diethylene glycol dimethyl ether , Dicyclohexyl-18-chloro-6, ethers such as methyl carbitol, ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate , Propylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphate triamide, phosphate Acids and acid derivatives such as limethyl, acetate Examples include nitriles such as lilyl, propionitrile, succinonitrile, and benzonitrile; nitrile compounds such as nitromethane and nitrobenzene; sulfur-containing compounds such as dimethyl sulfoxide; and water. These may be used as appropriate, if necessary.

In the case of using a solvent, generally, as the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, as the amount decreases, it becomes difficult to uniformly heat and stir or a side reaction easily occurs. Therefore, 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 general-purpose methods such as thin-layer chromatography, gas chromatography, and high-performance liquid chromatography. Any of the coumarin derivatives represented by Chemical Formulas 1 to 62 can be produced in a desired amount by this method. In addition, all of the compounds represented by the general formulas 6 and 7 can be obtained according to a general-purpose method for preparing an analogous compound. A coumarin derivative in which R ₇ in the general formula 1 is a substituent Although the body is generally low in yield, for example, James Earl 'Selim et al.,' Indian Journal 'Shibu' Heterocyclic 'Chemistry', Vol. 6, pp. 95-98 (1 996) or can be prepared according to that method.

The compound represented by the general formula 5 is, for example, supervised by Munio Kotake, “Daikaku Kagaku Kagaku”, 1959, published by Asakura Shoten Co., Ltd., Volume 14 (I), 241 In accordance with the method described on page 269, a salicylaldehyde derivative represented by the general formula 8 having R, to R ₄ corresponding to the general formula 1 and R ₅ and R corresponding to the general formula 1 It can be prepared by reacting a 3-ethyl oxobutanoate derivative having ₆ with. On the other hand, the compound represented by the general formula 8 can be obtained, for example, according to the method described in the above-mentioned reference or according to the method described in Japanese Patent Publication No. 60-23336. formula 1 at the 3-position the Japan chemical Society of Kumari down derivative represented by the general formula 9 with R ₈ or R _{1 2} corresponding "new experimental chemistry course", 1 9 7 7 years, Maruzen Co., Ltd. It can be prepared by formylation by the Vilsmeier reaction described in Vol. 14, No. 14 (I 1), p.

—General formula 8:

General formula 9:

The coumarin derivative thus obtained may be used in the form of a reaction mixture depending on the application, but usually, prior to use, for example, dissolution, separation, gradient, filtration, extraction, concentration, and thin layer formation. Purified by general-purpose methods for purifying analogous compounds such as chromatography, column chromatography, gas chromatography, high-performance liquid chromatography, distillation, sublimation, crystallization, etc. Are applied in combination. When the coumarin derivative of the present invention is used in, for example, an organic EL device or a dye laser, it should be highly purified prior to use, for example, by a method such as distillation, crystallization and / or sublimation. Is desirable. Of these, sublimation facilitates the production of high-purity crystals in a single operation, reduces the loss of the coumarin derivative during the operation, and does not incorporate any solvent into the crystals. Especially excellent. The sublimation method to be applied may be the normal pressure sublimation method or the reduced pressure sublimation method, but usually the latter reduced pressure sublimation method is applied. To vacuum sublimation of Kumari down derivative of the present invention, for example, charged Kumari down derivatives q.s. into the sublimation purification apparatus 1 0 in the apparatus - below ² T orr reduced pressure, preferably, 1 0- ³ T Heat at a temperature as low as possible below the melting point while keeping the temperature below 0 rr so that the coumarin derivative does not decompose. When the purity of the coumarin derivative to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of vacuum or heating temperature so that no impurities are mixed, and when the coumarin derivative is difficult to sublimate. Sublimation by passing an inert gas such as a rare gas into the sublimation purification equipment. To promote. The size of the crystals obtained by sublimation can be adjusted by adjusting the temperature of the condensing surface in the sublimation purification equipment, keeping the condensing surface slightly lower than the heating temperature and gradually crystallizing. A relatively large crystal is obtained.

The use of the coumarin derivative according to the present invention will be described. As described above, the coumarin derivative of the present invention has an emission maximum in the visible region and emits red to orange fluorescent light when excited. By appropriately combining with a host compound, it can be used very advantageously as a luminescent agent for an organic EL device.

—As described above, the coumarin derivative represented by the general formula 1 has an emission maximum in the visible region, more specifically, in the red or near red region, and forms a stable thin film in a glassy state. Therefore, when used alone or in combination with another luminescent compound, it can be used very advantageously as a luminescent agent for an organic EL device. The organic EL device according to the present invention means an electroluminescent device using such a luminescent agent in general, and in particular, an anode for applying a positive voltage, a cathode for applying a negative voltage, and a recombination of holes and electrons. A light-emitting layer that emits light by letting it emit light, a hole injection / transport layer that injects and transports holes from the anode, and an electron injection Z transport layer that injects and transports electrons from the cathode, if necessary. Single-layer and stacked organic EL devices are important applications.

As is well known, the operation of an organic EL element 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. It consists of a process of generating a singlet exciton or a triplet exciton and a process of emitting light from the exciton, and these processes are essentially the same in both single-layer and stacked organic EL devices. However, in the single-layer organic EL device, the characteristics of the above four processes can be improved only by changing the molecular structure of the light-emitting compound. In a layered organic EL device, the functions required in each process are shared among multiple materials and each material can be optimized independently. Also, it is easier to achieve the desired performance if it is configured as a stacked type.

Therefore, the organic EL device of the present invention will be described by taking a stacked organic EL device as an example. FIG. 1 is a schematic diagram of a stacked organic EL device according to the present invention, where 1 is a substrate, Usually, glass such as soda glass, barium silicate glass, and aluminosilicate glass, or a substrate material such as plastic or ceramic is used. Preferred substrate materials are transparent glass and plastic, and opaque ceramics such as silicon are used in combination with transparent electrodes.

Reference numeral 2 denotes an anode, which is made of a metal or a conductive compound which is electrically low-resistive and has a high light transmittance over the entire visible region, usually by vacuum evaporation, screen ring, or chemical vapor deposition. CVD), Atomic Layer Epitaxy (ALE), coating, dipping, etc., so that it is in close contact with one side of the substrate 1 so that the resistivity at the anode 2 is 1 kQZ or less. It is formed by forming a film having a thickness of 10 to 100 nm, preferably 50 to 500 nm. Examples of such conductive materials include metals or alloys such as gold, platinum, aluminum, and nickel, tin oxide, indium oxide, and mixed systems of tin oxide and indium (hereinafter, abbreviated as ITO j). A metal oxide or a conductive ligomer or polymer having repeating units of aniline, thiocyanphen, pyrrole, etc. is used, of which ITO having a low resistivity is easily used. In addition to being obtained, a fine pattern can be easily formed by etching using an acid.

Reference numeral 3 denotes a hole injecting / transporting layer, which is usually brought into close contact with the anode 2 by a method similar to that for the anode 2 so that the material for the hole injecting / transporting layer has a thickness of 1 to 1,0,0. It is formed by forming a film to a thickness of 100 nm. As a hole injection / transport layer timber, in order makes it easier to transport and hole injection from the anode 2, low ionization potential, and, for example, Te field under the smell of 1 0 ⁴ to 1 0 ⁶ VZ cm , at a minimum, which exhibits a hole mobility of 1 0- ⁶ cm ² V ■ s is desirable. Individual hole injecting / transporting layer materials are commonly used in organic EL devices, for example, aromatic tertiary amines, styrylamines, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazolines Derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amine-substituted chalcone derivatives, genoxazole derivatives, styryllanthracene derivatives, fulgenrenon derivatives, hydrazone derivatives, stilbene derivatives, and the like. These are used in combination.

Reference numeral 4 denotes a light-emitting layer, which is usually attached to the hole injection / transport layer 3 in the same manner as that for the anode 2 so that one or a plurality of light-emitting compounds are separated into a single layer or two layers. It is formed by forming a film having a thickness of 1 to 1, OOO nm, and preferably a thickness of 0 to 200 nm. As the luminescent compound, a coumarin derivative represented by the general formula 1 may be used alone, or a coumarin derivative represented by the general formula 1 as a guest compound may be used in a thin film state as a host compound. One or more other luminescent compounds that provide luminescence quantum efficiency are used. Examples of the individual luminescent compounds that can be used in combination with the coumarin derivative of the present invention include, for example, oxathiazole, phenanthrene, triazole, quinacridone, luprene or a derivative thereof, a quinolinol metal complex, and distyrylaryl. Examples include a monolen derivative or a spiro compound thereof, and a diphenylanthracene derivative. Of these, distyryl arylene derivatives, their spiro compounds, and diphenylanthracene derivatives usually have wavelengths of from 330 to 5 It has an emission maximum such as a fluorescence maximum in the blue or green region of 10 nm, and its emission wavelength is substantially the same as the absorption maximum wavelength of the coumarin derivative according to the present invention (usually 470 to 510 nm). Overlap. Therefore, when these luminescent compounds having an emission maximum in the blue or green range are used in the light-emitting layer 4 in combination with the coumarin derivative of the present invention, the former excitation energy is more efficient than the coumarin derivative of the present invention. Therefore, it functions as an extremely effective host compound in an organic EL device that emits red to orange light or white light described below.

The most desirable host compound for emitting red to orange light is a quinolinol metal complex, and the quinolinol metal complex referred to in the present invention is a compound having a quinolinol as a ligand and an organic EL element. It means all metal complexes that can be used as host compounds. Preferred quinolinol metal complexes are metal complexes having 8-quinolinols as ligands, such as aluminum, zinc, beryllium, magnesium, indium, lithium, calcium, calcium, and the like. And those having a central atom of a metal of Group 1, Group 2, Group 12 or Group 13 or an oxide thereof in the periodic table. In addition, 8-quinolinols as ligands may be located at a site other than the 8-position to which a hydroxy group is bonded, for example, a halogen group such as a chloro group, a chloro group or a bromo group. , Methyl, trifluoromethyl, ethyl, propyl, and other short-chain alkyl groups or haloalkyl groups, alkoxy groups, such as methoxy, ethoxy, and propoxy groups, and methoxycarbonyl groups. And an alkoxycarbonyl group such as an ethoxycarbonyl group, and one or more substituents such as a cyano group, a nitro group, a sulfonyl group and a hydroxy group.

Examples of the individual quinolinol metal complexes include, for example, tris (8-quinolinolate) aluminum, tris (3,4-dimethyl-8-quinolinolate) Aluminum, tris (4-methyl-18-quinolinolate) aluminum, tris (4-methoxy8-quinolinolate) aluminum, tris (4,5-dimethyl-18-quinoline) Aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, tris (5-chloro-8-quinolineolate) aluminum, tris (5-bromo-8-quinolineolate) aluminum, metal Squirrel (5,7-dichloro-8-quinolinolate) aluminum, tris (5-cyano-8-quinolinolate) aluminum, tris (5-sulfonyl-8-quinolinolate) aluminum), Tris (5-propyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolino) Aluminum complex such as 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-cyanquinolinolate) zinc, bis (3,4-dimethyl-8-quinolinolate) zinc, Bis (4,6—dimethyl-18-quinolinolate) zinc, bis (5—chloro-8-quinolinolate) zinc, bis (5,7-dichloro-8-quinolinolate) zinc, etc. Bis (8-quinolinolate) beryllium, bis (2-methyl-18-quinolinolate) beryllium, bis (2,4-dimethyl-8-quinolino) Beryllium, bis (2-methyl-5-chloro-8-quinolinolate) beryllium, bis (2-methyl-5-cyanquinolinolate) beryllium, bis (3,4-dimethyl-1-yl) Beryllium, bis (4, 6-dimethyl-8-quinolinolate) beryllium, bis (5-chloro-8-quinolinolate) beryllium, etc. Um complex, bis (8-quinolinolate) magnesium, bis (2-methyl-8-quinolinolate) magnesium, bis (2,4-dimethyl) — 8—Quinolinolate) Magnesium, bis (2-methyl-1-5-cyano-18—quinolinolate) magnesium, bis (3,4—dimethyl-18—quinolinolate) magnesium, bis (4, Magnesium complex such as magnesium, bis (5-chloro-8-quinolinolate) magnesium, bis (5,7-dichloro-8-quinolinolate) magnesium Indium complexes such as tris (8-quinolinol) indium; gallium complexes such as tris (5-chloro-8-quinoline) gallium; bis (5—quinoline 18—quino) Linolate) Calcium complexes such as calcium are exemplified, but these are merely examples, and the quinolinol metal complex referred to in the present invention is not limited. It is not limited to have it. When the quinolinol metal complex has two or more ligands in the molecule, these ligands may be the same or different. When the coumarin derivative represented by the general formula 1 is used as a guest compound, it usually depends on the type of the host compound to be combined, but usually 0.01 mol% or more based on the host compound. Desirably, it is added in the range of 0.1 to 10 mol%.

Reference numeral 5 denotes an electron-injecting Z transport layer, which is usually an organic compound having a high electron affinity by being brought into close contact with the light-emitting layer 4 by the same method as that for the anode 2 to emit light in the red or near red region. It does not absorb, for example, the same compound as in the light-emitting layer 4, or a cyclic ketone or a derivative thereof such as benzoquinone, anthraquinone, or fullerenone, a silazane derivative, or an anily. It is formed by forming one or more conductive oligomers or polymers having a repeating unit of thiophene, thiophene, pyrrole or the like to a thickness of 10 to 500 nm. When a plurality of materials for the electron injection / transport layer are used, even if the materials for the electron injection / transport layers are uniformly mixed to form a single layer, the materials for the electron injection / transport layer can be mixed without mixing. Adjacent to May be formed in a plurality of layers.

Reference numeral 6 denotes a cathode, which is usually in close contact with the electron injection / transport layer 5 and has a lower work function (typically 6 eV or less) than the compound used in the electron injection / transport layer 5, for example, lithium, magnesium, and calcium. Metal, metal oxide such as silver, copper, aluminum, indium, or indium, or a conductive compound, alone or in combination, or a buffer layer such as copper lid cyanine and an ITO electrode. Are combined to form a cathode. The thickness of the cathode 6 is not particularly limited, and is usually 1 O nm or more so that the resistivity is 1 / port or less, while taking into account the conductivity, manufacturing cost, overall device thickness, light transmittance, and the like. Preferably, it is set to 50 to 500 nm. In order to improve the adhesion between the cathode 6 and the electron injection / transport layer 5, if necessary, for example, an aromatic diamine compound, a quinacridone compound, a naphthacene compound, an organic silicon compound, An interface layer containing an organic phosphorus compound or the like, or a thin film of an alkali metal or an alkaline earth metal may be provided to improve electron injection efficiency.

As described above, the organic EL device of the present invention comprises an anode 2, a light-emitting layer 4, and a cathode 6, a hole injection / transport layer 3, and an electron injection / transport layer 5, if necessary. Can be manufactured by forming them integrally while adhering to an adjacent layer. The hitting To form each layer, oxidation and decomposition of the organic compounds, further, to suppress the like adsorbed oxygen and water to a minimum, under high vacuum, in particular, consistently below 1 0- ⁵ T 0 rr It is desirable to work. In forming the light-emitting layer 4, the host compound and the coumarin derivative of the present invention are mixed in advance at a predetermined ratio, or the heating rates of the two in vacuum deposition are made independent of each other. Thus, the mixing ratio of the two to be deposited on the light emitting layer 4 is adjusted. The organic EL device thus constructed is designed to minimize degradation in the operating environment. It is desirable that a part or the whole be sealed with a sealing glass or a metal cap in an inert gas atmosphere, or covered with a protective layer of an ultraviolet curable resin or the like.

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 may be configured to intermittently apply a relatively high voltage pulse voltage or a relatively low voltage depending on the application. The non-pulse voltage (typically 2 to 50 V) is continuously applied for driving. The organic EL device of the present invention emits light only when the potential of the anode is higher than that of the cathode. Therefore, the voltage applied to the organic EL device of the present invention may be DC or AC, 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, increases or decreases in luminance 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. 5, when a voltage is applied between the anode 2 and the cathode 6, holes injected from the anode 2 pass through the hole injection / transport layer 3 to the light emitting layer 4, and to the cathode 4. The electrons injected from 6 reach the light emitting layer 4 via the electron injection / transport layer 5 respectively. As a result, the recombination of holes and electrons occurs in the light emitting layer 4, and the desired red or orange light is emitted from the excited coumarin derivative through the anode 2 and the substrate から. Becomes The organic EL device of the present invention usually has a wavelength of 550 nm or more, and more specifically, 550 to 650, although it depends on the light-emitting characteristics of the coumarin derivative and the type of host compound used in combination. It has an emission maximum in the red or near red range of nm. In addition, the luminescence usually has X in the range of 0.4 to 0.7 and y in the range of 0.3 to 0.6 in the xy chromaticity coordinates.

Further, as described above, the coumarin derivative used in the present invention emits red to orange light in the organic EL device, and therefore, in the light emitting layer 4, a blue region or green light capable of emitting complementary blue to green light is emitted. Light emitting pole in the area By using another light emitting compound having a large size as described above in combination, white light can be emitted from the organic EL element. Specifically, in forming the light-emitting layer 4, the layer containing the coumarin derivative and the layer containing the coumarin derivative are adjusted with the color purity of white light as an index, for example, while adjusting the film thickness and / or the content of the luminescent compound. A single-layer light-emitting layer 4 is formed by laminating a layer containing a light-emitting compound that emits green light, or by mixing a mixture of both with an appropriately adjusted mixing ratio. Although it depends on the kind of the luminescent compound to be combined, the white light thus obtained usually has X in the range of 0.25 to 0.4, and y in the xy chromaticity coordinates. It is in the range of 5 to 0.4.

Since the organic EL device of the present invention is excellent in luminous efficiency and durability, it has various uses in luminous bodies and information display devices for visually displaying information. The luminous body using the organic EL element of the present invention as a light source has low power consumption and can be configured in a lightweight panel shape. Therefore, in addition to a general illumination light source, for example, a liquid crystal element, a copying machine, Equipment, electrophotographic equipment, computers and their applied equipment, industrial control equipment, electronic measuring equipment, analytical equipment, general instruments, communication equipment, medical electronic measuring equipment, general consumer and commercial electronic equipment, and It is extremely useful as an energy-saving and space-saving light source and information display element in vehicles, ships, aircraft, spacecraft, and other general equipment, aircraft control equipment, interiors, signboards, and signs. The organic EL device of the present invention is used, if necessary, in combination with a filter that blocks light having a wavelength of 585 nm or less, and usually formed into a panel shape according to the intended use. The organic EL device of the present invention is used for lighting equipment, for example, dashboards for vehicles, ships, aircraft, spacecrafts, etc., computer terminals, television receivers, recorders, game machines, watches, telephones, and communication devices. When used for information display devices such as car navigation devices, oscilloscopes, radars, sonars, signboards, signs, etc. The organic EL device of the present invention that emits white light alone or in combination with an organic EL device that emits blue or green light, as required, can be used as a general-purpose simple matrix method or active matrix. Drive by applying the trick method.

Further, in order to use the coumarin derivative of the present invention as a laser active substance, it is necessary to purify it in the same manner as in the case of constructing a known dye-based laser oscillator, dissolve it in an appropriate solvent, and if necessary, After adjusting the pH to an appropriate level, it is sealed in a dye cell in a laser oscillator. The coumarin derivative of the present invention not only provides an amplification gain in an extremely wide wavelength range in the visible region, but also has high light resistance and is hardly deteriorated even when used for a long time, as compared with known coumarin derivatives. There is.

Furthermore, since the coumarin derivative of the present invention has an absorption maximum in the visible region and substantially absorbs visible light, a material for polymerizing the polymerizable compound by exposing it to visible light and a solar cell are disclosed. It has a wide variety of uses as a material for sensitization, a chromaticity adjusting material for optical filters, and a material for dyeing various kinds of clothing. In particular, most of the coumarin derivatives of the present invention have absorption maximum wavelengths such as gas lasers such as argon ion lasers and krypton ion lasers, semiconductor lasers such as CdS lasers, and distributed feedback. Because it is close to the oscillation wavelength of general-purpose visible lasers having oscillation lines at wavelengths of 450 to 550 nm, including solid-state lasers such as solid-state lasers, such as a solid-state or distributed Bragg reflection type Nd-YAG laser, By blending it as a photosensitizer with a photopolymerizable composition using such a visible laser as an exposure light source, it can be used in the fields of information recording such as facsimile, copier, printer, etc., flexographic plate making, gravure plate making, etc. It can be used extremely advantageously in the field of printing, and in the field of printed circuits such as photo resists. Further, the coumarin derivative of the present invention may be used, if necessary, together with one or more other materials that absorb light in the ultraviolet, visible, and / or infrared regions. Drapes, laces, casements, prints, Venetian blinds, roll screens, shutters, goodwill, blankets, futons, futons, futon covers, futon cotton, sheets, cushions, pillows, pillowcases, cushions, pine Rugs, carpets, sleeping bags, tents, car interior materials, built-in bedding products such as window glass and window glass, disposable diapers, diaper covers, eyeglasses, monocles, rowets and other health supplies, shoe insoles, Shoe lining, shinji, furoshiki, umbrella, umbrellas, stuffed animals and lighting equipment, for example, CRT displays, liquid crystal displays Filters for information display devices such as television receivers and personal computers using electroluminescent displays, plasma displays, etc., panels and screens, sunglasses, sunroofs, PET bottles, storages, greenhouses, Viewing windows such as cold gauze, optical fiber, prepaid card, electronic range, open, etc., and when using these materials for packaging, filling or storing packaging materials, filling materials, containers, etc. Not only can we prevent or reduce obstacles and inconveniences caused by environmental light such as natural light or artificial light on the goods, but we can also adjust the color, color tone, texture, etc. of the goods, and reflect the light transmitted from the goods. There is a real benefit that you can achieve the desired color balance.

Hereinafter, embodiments of the present invention will be described based on examples. Example 1 Coumarin derivative

An appropriate amount of black form is placed in a reaction vessel, 2.0 g of the compound represented by the chemical formula 63 and 1.8 g of the compound represented by the formula 64 are added, and the mixture is heated and dissolved. mI and 1.1 ml of acetic acid were added, and the mixture was heated under reflux for 4 hours. After concentrating the reaction mixture, ethanol was added and the precipitated crude crystals were collected Recrystallization using a form / ethanol mixture yielded 1.2 g of brownish red crystals of the coumarin derivative represented by the chemical formula 5.

Formula 63:

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 250 to 255 ° C. Furthermore, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivatives of this example showed wavelengths of 501 nm and 6 nm, respectively. It showed an absorption maximum and a fluorescence maximum at 49 nm. Further, when the ¹ H—nuclear magnetic resonance spectrum (hereinafter abbreviated as “ ¹ H—NMR spectrum”) of the dimethyl d ₆ sulfoxide solution was measured, the chemical shift 6 (ρ ρ m, TMS) is 1.26 (6H, s), 1.47 (6H, s), 1.70 (2H, t), 1.76 (2H, t), 3.5 0 to 3.90 (4H, m), 6.78 (1H, d), 6.86 (1H, dd), 7.39 (Ί, s), 7.60 (1H, d) .7.80 (1H, d), 8.02 (1H, d), 8.23 (1H, s), 8.31 (1H, s) And 8.6 1 (1 H, s) A peak was observed at the position.

The coumarin derivative of this example, which has an absorption maximum and a fluorescence maximum in the visible region, has a wide variety of uses in various fields requiring organic compounds having such properties, including luminescent agents for organic EL devices. . Example 2 Coumarin derivative

To a reaction vessel, add an appropriate amount of black form, add 2.0 g of the compound represented by the chemical formula 65 and 2.3 g of the compound represented by the formula 66, and dissolve by heating. 5 ml and 1.4 ml of acetic acid were added, and the mixture was heated under reflux for 4 hours. After concentrating the reaction mixture, ethanol was added, and the precipitated crude crystals were recrystallized using a mixed solution of chloroform and ethanol, and a bright green-red crystal of a coumarin derivative represented by the chemical formula 2 was obtained. g was obtained. Chemical formula 65

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 240 to 245 ° C. Furthermore, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example was found to have a wavelength of 479 nm. And the absorption maximum and the fluorescence maximum at 63 nm. Further, when the ¹ H—NMR spectrum of the ^1- d solution of the pore-form was measured, the chemical shift δ (ppm, TMS) was 1.14 (6H, t), 3.48 (4 H, q), 6.60 (1H, d), 6.75 to 6.85 (3H, m), 6.86 (1H, dd), 7.52 (1H , D), 7.61 (1H, d), 7.80 (Ί, d), 8.04 (1H, d), 8.33 (1H, s), and 8. A peak was observed at the position of 6 1 (1 H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 3 Coumarin derivative

The reaction was carried out in the same manner as in Example 1 except that the compound represented by Chemical Formula 66 was used instead of the compound represented by Chemical Formula 64, and then the reaction mixture was purified. A bright red crystal of a coumarin derivative was obtained.

As measured by a conventional method, the melting point of the coumarin derivative of this example was 235 ° C. Furthermore, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the conventional methods, the coumarin derivative of this example had wavelengths of 505 nm and 675 nm, respectively. Shows the absorption maximum and the fluorescence maximum. In addition, the ¹ H-NMR spectrum of a ¹ d solution of formaldehyde in black mouth was measured, and the shift 5 (ppm, TMS) of the histological shift was 1.24 (6 H, t), 3.45 ( 4H, q), 6.48 (1H, d), 6.61 (1H, dd), 7.30 to 7.45 (3H, m), 7.60 to 7 70 (2H, m), 7.82 (1H, d), 7.90 (1H, s), 8.13 (Ί, s) and 8.50 (1H , S) Work was observed.

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 4 Coumarin derivative

Reaction was performed in the same manner as in Example 2 except that the compound represented by Chemical Formula 64 was used instead of the compound represented by Chemical Formula 66, and then the reaction mixture was purified. Light orange crystals of the coumarin derivative were obtained.

The melting point of the coumarin derivative of this example was 278 ° C. as measured according to a conventional method. Further, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the usual methods, the coumarin derivative of this example was found to have wavelengths of 474 nm and 606 η, respectively. m shows the absorption maximum and the fluorescence maximum. Further, when the ¹ H-NMR spectrum of the dimethyl 0) ₆ sulfoxide solution was measured, the chemical shift δ (ρ pm, TMS) was 1.31 (6 H, s) and 1. 5 6 (6 H, s), 1.7

6 (2H, t), 1.81 (2H, t), 3.29 (2H, t), 3.3

7 (2H, t), 7.15 (1H, s), 7.30 to 7.45 (2H, m), 7.59 to 7.64 (2H, m) , 7.85 (1H, s), 7.

Peaks were observed at the positions of 85 (1H, d), 8.15 (1H, d) and 8.51 (1H, s).

The coumarin derivative of this example, which has an absorption maximum and a fluorescence maximum in the visible region, has a wide variety of uses in various fields requiring an organic compound having such properties, such as a luminescent agent for an organic EL device. Having. Example 5 Coumarin derivative

The reaction was carried out in the same manner as in Example 1 except that the compound represented by Chemical Formula 67 was used instead of the compound represented by Chemical Formula 64, and then the reaction mixture was purified. A dark green crystal of the coumarin derivative was obtained.

As measured by a conventional method, the melting point of the coumarin derivative of this example was 278 to 284 ° C. Further, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example was found to have wavelengths of 504 nm and 6778, respectively. The absorption maximum and the fluorescence maximum were shown at nm. Further, when the ¹ H-NMR spectrum of the solution of the port-form solution was measured, the chemical shift δ (ppm, TMS) was 1.31 (6H, s), 1.55 (6 H, s), 1.73 to 1.80 (4H, m), 3.28 (2H, t), 3.37 (2H, t), 3.99 (3H , S), 7.15 (1H, s), 7.85 (1H, d), 7.86 (1H, s), 8.11 (1H, d), and 8. A peak was observed at the position of 47 (1H, s).

The coumarin derivative of this example, which has an absorption maximum and a fluorescence maximum in the visible region, can be used in a wide variety of applications in various fields that require organic compounds having such properties, including organic luminescent agents. Have. Example 6 Coumarin derivative

The reaction was carried out in the same manner as in Example 2 except that the compound represented by Chemical Formula 68 was used instead of the compound represented by Chemical Formula 66, and then the reaction mixture was purified. A bright red-brown crystal of the coumarin derivative was obtained.

The melting point of the coumarin derivative of this example was 289 to 294 ° C. as measured according to a conventional method. Furthermore, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the usual methods, the coumarin derivatives of this example showed wavelengths of 484 nm and 649 nm, respectively. The absorption maximum and the fluorescence maximum were shown at nm. In addition, when the NMR spectrum of the chromate-form / d / trifluoroacetic acid solution was measured, the chemical shift (5 (ppm, TMS)) was 1.23 (6H, t), 3.75 (4H, q), 7.43 (1H, d), 7.56 (1H, d), 7.62 (1H, dd), 7.72 (1 H, dd), 7.77 (1H, d), 7.82 (1H, d), 7.93 (1H, d), 8.29 (1H, s), 8 Peaks were observed at 40 (1H, d) and 8.70 (1H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is widely used in various fields that require an organic compound having such properties, including a luminescent agent for an organic E1 element. It has applications. Example 7 Coumarin derivative

The reaction mixture was purified in the same manner as in Example 2 except that the compound represented by Chemical Formula 67 was used instead of the compound represented by Chemical Formula 66, and the reaction mixture was purified. An orange crystal of the coumarin derivative was obtained.

As measured by a conventional method, the melting point of the coumarin derivative of this example was 2443 to 251 ° C. Furthermore, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the usual methods, the coumarin derivative of this example was found to have wavelengths of 480 nm and 623, respectively. The absorption maximum and the fluorescence maximum were shown at nm. Further, when the ¹ H-NMR spectrum of the clot form-d solution was measured, the chemical shift <5 (ppm, TMS) was found to be 1.23 (6H, i :), 3.64 (4 H, q), 4.00 (3H, s), 7.30 (5H, m), 7.72 (1H, d), 7.81 (1H, d), 8 Peaks were observed at positions 12 (1H, s), 8.32 (1H, d) and 8.64 (1H, s).

The coumarin derivative of this example, which has an absorption maximum and a fluorescence maximum in the visible region, can be used in a wide variety of applications in various fields that require organic compounds having such properties, including organic luminescent agents. Have. Example 8 Coumarin derivative

The reaction was carried out in the same manner as in Example 1 except that the compound represented by Chemical Formula 68 was used instead of the compound represented by Chemical Formula 64, and then the reaction mixture was purified. An orange crystal of the coumarin derivative was obtained. -The melting point of the coumarin derivative of this example was 248 to 251 ° C as measured according to a conventional method. In addition, the visible absorption spectrum When the torr (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured, the coumarin derivative of this example showed an absorption maximum and a fluorescence maximum at wavelengths of 509 nm and 582 nm, respectively. In addition, ¹ H-NMR spectrum of a ¹ d solution of the gel was measured to find that the chemical shift <5 (ppm, TMS) was 1.31 (6H, s) and 1.5. 6 (6H, s), 1.76 (2H, t), 1.81 (2H, t), 3.29 (2H, t), 3.38 (2H, t) ), 7.15 (1H, s), 7.33 (1H, d), 7.56 (1H, dd), 7.62 (1H, d), 7.83 Peaks were observed at (1H, s), 7.83 (1H, d), 8.12 (1H, d), and 8.40 (1H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 9 Coumarin derivative

The reaction was carried out in the same manner as in Example 以外 except that the compound represented by Chemical Formula 69 was used instead of the compound represented by Chemical Formula 64, and then the reaction mixture was purified. Black crystals of the coumarin derivative were obtained.

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 2 55 to 260 ° C. Furthermore, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example showed wavelengths of 511 nm and 564 nm, respectively. The absorption maximum and the fluorescence maximum were shown at nm. Further, when the ¹ H—NMR spectrum of the solution of the dye solution was measured, the chemical shift <5 (ppm, TMS) was 1.31 (6H, s) and 1.56 (6H). , S), 1.76 to 1.81 (4H, m), 3.29 (2H, t), 3.38 (2H, t), 7.14 (1H, s), 7.72 (1H, d), 7.83 (1H, s), 7.84 (1H, d), 7.96 (1H, d), 8.0 Peaks were observed at positions 6 (1H, d) and 8.33 (1H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 10 Coumarin derivative

The reaction was carried out in the same manner as in Example 2 except that the compound represented by Chemical Formula 69 was used instead of the compound represented by Chemical Formula 66, and then the reaction mixture was purified. A dark brown crystal of the coumarin derivative was obtained.

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 2

68 to 272 ° C. Further, when the visible absorption spectrum (methylene chloride solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example was found to have wavelengths of 490 nm and 581, respectively. The absorption maximum and the fluorescence maximum were shown at nm. Further, N, ¹ of N- di-methyl formamidine doughs d ₇ solution H -. NMR spectrum and the measured time, I匕学shift "5 (ppm, TMS) is 1 3 1 (6 H, t), 3. 6 1 (4H, q), 6.71 (1H, d), 6.95 (1H, dd), 7.67 (1H, d), 7.85 ), 8.05 (Ί Η, d), 8.36 (2H, m), 8.45 (1H, s), and 8.69 (1H, s). Was observed.

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 11 1 Coumarin derivative

The reaction was carried out in the same manner as in Example 2 except that the compound represented by Chemical Formula 70 was used instead of the compound represented by Chemical Formula 66, and then the reaction mixture was purified. A red crystal of the coumarin derivative was obtained.

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 288 to 292 ° C. Furthermore, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example showed wavelengths of 476 nm and 60 nm, respectively. The absorption maximum and the fluorescence maximum were shown at 3 nm. In addition, the ¹ H—NMR spectrum of a solution of porcine form 1d / trifluroacetic acid was measured. The chemical shift δ (ppm, TMS) was 1.23 (6H, i :), 3.74 (4H, q), 3.966 (1H, s), 3.99 (1H, s), 6.37 (1H, d), 6.52 (1H, d), 7.53 (1H, d), 7.59 (1H, dd) , 7.81 (1 Hd), 7.91 (1H, d), 8.27 (1H, s), 8.48 (1H, d) and 9.08 (1 A peak was observed at the position of H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region has a wide variety of uses in various fields requiring an organic compound having such properties, including a luminescent agent for an organic EL device. . Example 12 Coumarin derivative

Either one of the 11 types of coumarin derivatives obtained by the methods of Examples 1 to 11 was charged into a water-cooled sublimation purification apparatus, and heated in a conventional manner while maintaining the inside of the apparatus under reduced pressure. Sublimated and purified. The coumarin derivative of this example is extremely useful in organic EL devices and dye lasers that require high-purity luminescent compounds.

Although the coumarin derivative of the present invention has slightly different charging conditions and yields depending on the structure, for example, all of the examples including those represented by the chemical formulas 1 to 62 other than those described above were used in Examples. A desired amount can be produced by the methods of Examples 1 to 12 or according to those methods. Example 13 Luminescent agent for organic EL device

In a reaction vessel, add an appropriate amount of black-mouthed form, add 5.1 g of the compound represented by the chemical formula 71 and 6.0 g of the compound represented by the chemical formula 72, and dissolve by heating. m I and 2.6 m I of acetic acid were added, and the mixture was heated under reflux for 6 hours. After concentrating the reaction mixture, ethanol was added, and the precipitated crude crystals were recrystallized using a mixed solution of chloroform and ethanol to obtain 3.4 g of red crystals of a coumarin derivative represented by the formula (7). Was done.

Chemical formula 71:

Chemical formula 72

The melting point of the coumarin derivative of this example was 263 ° C. as measured according to a conventional method. Furthermore, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the conventional methods, the coumarin derivative of this example was found to have a wavelength of 505 nm and a wavelength of 613 η, respectively. m shows the absorption maximum and the fluorescence maximum.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for organic EL devices. Example 14 Luminescent Agent for Organic EL Device

An appropriate amount of chloroform is placed in a reaction vessel, 1.9 g of the compound represented by the formula 73 and 4.0 g of the compound represented by the formula 74 are added, and the mixture is heated and dissolved. ml and 1.4 ml of acetic acid were added, and the mixture was heated and transferred for 5 hours. After concentrating the reaction mixture, ethanol was added and the precipitated crude crystals were collected When recrystallized from a mixed solution of formnoenol, 2.0 g of red crystals of the coumarin derivative represented by the chemical formula 11 was obtained.

Chemical formula 73:

Chemical formula 74:

The melting point of the coumarin derivative of this example was 285 ° C. as measured by a conventional method. Furthermore, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the conventional methods, the coumarin derivative of this example was found to have a wavelength of 503 nm and a wavelength of 568 η, respectively. m shows the absorption maximum and the fluorescence maximum.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device. Example 15 Organic device EL luminescent agent for EL element

To a reaction vessel, take an appropriate amount of a stoichiometric form, add 2.0 g of the compound represented by the chemical formula 71 and 1.8 g of the compound represented by the chemical formula 75, and dissolve by heating. 8 ml and 1.1 ml of acetic acid were added, and the mixture was refluxed for 4 hours. After concentrating the reaction mixture, ethanol was added, and the precipitated crude crystals were recrystallized using a mixed solution of formaldehyde and ethanol to obtain 1.2 g of brownish red crystals of the coumarin derivative represented by the formula (5). Obtained. Chemical formula 75

When measured according to a conventional method, the melting point of the coumarin derivative of this example was in the range of 250 to 255 ° C. Furthermore, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example was found to have wavelengths of 501 nm and 64 nm, respectively. It showed an absorption maximum and a fluorescence maximum at 9 nm.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device. Example 16 Organic EL Device Luminescent Agent

To a reaction vessel, add an appropriate amount of black-mouthed form, add 2.0 g of the compound represented by the chemical formula 73 and 2.3 g of the compound represented by the formula 76, dissolve by heating, and then add 2.5 ml of piperidine. And 1.4 ml of acetic acid, and the mixture was heated under reflux for 4 hours. After concentrating the reaction mixture, ethanol was added, and the precipitated crude crystals were recrystallized using a mixture of chloroform and ethanol to obtain 1.3 g of a bright green-red crystal of a coumarin derivative represented by the formula (2). Was done.

When measured according to a conventional method, the melting point of the coumarin derivative of this example was 240 to 245 ° C. In addition, the visible absorption spectrum Toluene (methanol solution) and fluorescence spectrum (methylene chloride solution) were measured, and the coumarin derivative of this example showed an absorption maximum and a fluorescence maximum at wavelengths of 479 nm and 623 nm, respectively. .

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device. Example 17 Organic EL device luminescent agent

The reaction and purification were carried out in the same manner as in Example 13 except that the compound represented by Chemical Formula 76 was used instead of the compound represented by Chemical Formula 72, and the brightness of the coumarin derivative represented by Chemical Formula 3 was determined. A red crystal was obtained.

As measured by a conventional method, the melting point of the coumarin derivative of this example was 235 ° C. Further, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example was found to have a wavelength of 505 nm and a wavelength of 675 η, respectively. m shows the absorption maximum and the fluorescence maximum.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device. Example 1 8 Luminescent agent for organic EL device

The reaction and purification were carried out in the same manner as in Example 14 except that the compound represented by Chemical Formula 75 was used instead of the compound represented by Chemical Formula 74. Orange crystals were obtained.

55 ° C. Further, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to a conventional method, the coumarin derivative of this example showed wavelengths of 474 nm and 60 nm, respectively. 4 η m shows the absorption maximum and the fluorescence maximum.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device. Example 1 9 Luminescent agent for organic EL device

The reaction and purification were conducted in the same manner as in Example 13 except that the compound represented by Chemical Formula 73 was used instead of the compound represented by Chemical Formula 71, and the brightness of the coumarin derivative represented by Chemical Formula 6 was determined. Red-purple crystals were obtained.

The melting point of the coumarin derivative of this example was 278 ° C. as measured according to a conventional method. Further, when the visible absorption spectrum (methanol solution) and the fluorescence spectrum (methylene chloride solution) were measured according to the usual methods, the coumarin derivative of this example was found to have wavelengths of 490 nm and 566 η, respectively. m shows the absorption maximum and the fluorescence maximum.

The coumarin derivative of this example having excellent luminescence characteristics is extremely useful as a luminescent agent for an organic EL device.

Although the coumarin derivatives used in the present invention have slightly different charging conditions and yields depending on the structure, for example, those represented by Chemical Formula 1 to Chemical Formula 17 are all Examples 13 to It can be prepared by the method of Example 19 or according to those methods. Example 20 Organic EL device

Using the luminescent agent for an organic EL device of the present invention, a laminated organic EL device having the structure shown in FIG. 1 was produced.

A glass substrate 1 having a transparent ITO electrode with a thickness of 100 nm as an anode 2 patterned with a water vapor is ultrasonically cleaned with a detergent, pure water, acetone and ethanol, dried, and irradiated with ultraviolet light. After treatment with ozone, And fixed to the vacuum evaporation apparatus was evacuated to 1 0- ⁷ T orr. Next, a tetramer of triphenylamine represented by the chemical formula 77 was deposited on the surface of the glass substrate 1 having the IT0 electrode to a thickness of 60 nm to form a hole injection / transport layer 2. . Then, while monitoring with a film thickness sensor, one of the coumarin derivatives according to the present invention shown in Table 1 and tris (8-quinolinolate) aluminum were used as a light emitting agent at a weight ratio of 1: 100. After forming a light emitting layer 4 by co-evaporation to 20 nm, and further forming an electron injection / transport layer 5 by depositing tris (8-quinolinol) aluminum to a thickness of 40 nm, Lithium fluoride and aluminum were deposited in this order to a thickness of 0.5 nm and 160 nm, respectively, to form cathode 6. Thereafter, under a nitrogen atmosphere, the entire device was sealed using a glass plate and an ultraviolet curable resin to obtain four types of organic EL devices.

The emission spectrum of the organic EL device thus obtained was measured according to a conventional method, and the relationship between the emission luminance and the injection current density or the applied voltage was examined. Calculated. In addition, the relationship between the initial emission Brightness 3 0 0 cd emission brightness when set to Zm ² and the driving time Investigation and calculation of the lifetime (driving time at which the initial emission luminance is halved). Separately, a system was prepared using the compound represented by Formula 8 in place of the coumarin derivative, and this was treated in the same manner as above to serve as a control. Table 1 shows the results.

Table 1 Coumarin derivatives Emission maximum wavelength Luminescence Emission quantum efficiency Lifetime Remarks

m> (cd / m ² ) * ¹ (% (time) ' ²

Chemical formula 6 572 523.3 1.6 3900 The present invention

Chemical formula 7 587 491.9 1.7 3030

Chemical formula 11 557 371.2 1.1 1100 The present invention

Chemical formula 12 592 422.9 1.6 3300

Chemical formula 73 605 119.0 0.53 680

* 1 indicates a measured value when driven at a current density of 11 mA / cm ² .

* 2 indicates the half-life when driven at a constant current with an initial light emission luminance of 300 cd / m ² . As can be seen from the results in Table 1, when a DC voltage is applied, the organic EL device of this example emits red to orange light having a maximum emission in the red or near red region at a wavelength of 560 to 600 nm. Brought. According to the emission spectrum, each emission has a narrow half width of 90 to 100 nm, good color purity, and undesired emission from tris (8-quinolinelate) aluminum. Light emission on the short wavelength side was not substantially accompanied. Light emission was confirmed from around 2.5 V, and reached 30, 000 to 60, 000 cd / m ^{2 at 12} to 15. When the organic EL device of this example was driven at a constant current of 1 ImAZ cm ² , the emission luminance was about 370 to 520 cd / m ² . The emission quantum efficiency was as high as about 1.1 to 1.7%. The luminescence continued stably, and no partial dark spot (dark spot) was observed even after the lapse of 1,000 hours from the start of the luminescence. The half-life when driven at a constant current of 300 cd / m ² , which is a practical light emission luminance, was 1,000 hours or more in each case. The lifetime of the organic EL device using the coumarin compounds represented by the chemical formulas 6, 7 and 12 was particularly long, from about 3,000 to 4,000 hours. Incidentally, as can be seen from the results in Table 1, the organic EL device of the control showed slightly more reddish emission than the organic EL device of this example, but was significantly significant in terms of emission quantum efficiency and lifetime. Was inferior.

Separately, the chemical formula 6, every organic EL device using a coumarin emission derivative represented by Chemical Formula 7 and Chemical Formula 1 2, 1 1 m A / cm 2 at a constant current driving the light emission spectrum when measured respectively, their The X and Y chromaticity coordinates of the light emission were determined from the light emission spectrum. In addition, the emission spectrum was measured in the same manner with a filter that blocks light with a wavelength of 585 nm or less attached to the glass substrate of these organic EL elements, and the XY chromaticity coordinates of the emission were determined. did. At the same time, the chromaticity coordinates of the emission were determined for the control organic EL element. Table 2 shows the results. , Table 2 Coumarin derivatives Filter-No Fill

Chromaticity coordinates (x, y) Luminance (cd / m ² ) * ¹ Chromaticity coordinates (x, y) Luminance (cd / m ² ) *

Chemical formula 6 (0.458,0.508) 523.3 (0.619,0.376) 220.7 The present invention

Chemical formula 7 (0.464,0.484) 491.9 (0.629,0.367) 196.0 The present invention

Chemical formula 1 2 (0.509, 0.463) 422.9 (0.636, 0.361) 168.6

Chemical formula 7 8 (0.629,0.365) 119.0 Reference

* 1 indicates a measured value when driven at a current density of llmA / cm ² . As can be seen from the results in Table 2, the organic EL device of this example without a filter emitted red light close to orange. However, the luminescence By using a filter that blocks light below a wavelength of 585 nm, the chromaticity coordinates of red light (X = 0.67, y = 0.33) according to the standards of the National Television System Commission (NTSC) in the United States. ), And the brightness was as high as about 200 cd dZm ² . On the other hand, the organic EL element of the control, since the color purity of light emission is slightly better, but does not require a filter, emission luminance is small and 1 1 S cd Zm ^2, organic EL device of the present embodiment in combination with filter Did not reach. These test results show that the use of the luminescent agent of the present invention containing a coumarin derivative enables the realization of a high-efficiency and long-life red organic EL device that can withstand practical use, Example 21. Display panel

FIG. 2 schematically shows 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.

That is, first, on one side of the glass substrate 10 according to the method of the embodiment 20.

After forming the anode 14 using the 1 T O transparent electrode, the anode 14 is processed into a strip shape by a wet etching method. Next, a hole injection Z transport layer 16 and a light emitting layer 18 were sequentially formed according to the method of Example 20, and a cathode 20 was formed in a strip shape using a mechanical mask. (Not shown) and the organic EL element is sealed with an ultraviolet curable resin. In addition, in the display panel of this example, in order to suppress the temperature rise during use, the cathode

A heat sink or a cooling fan may be attached to the back side of the 20. Example 2 2 Information display device

FIG. 3 shows a display panel manufactured according to the method of Example 21. 1 is an example of an information display device. In FIG. 3, reference numeral 30 denotes a DC power supply having an output voltage of 4.5 V, and two booster circuits 32 and 34 are connected to its output terminal. The booster circuit 32 can supply a DC voltage in the range of 5 to 12 V, and its output terminal is connected to the driver circuit 36. The other booster circuit 34 is for supplying a constant voltage of 5 V to the microcomputer 38.

The microcomputer 38 has an IZO interface 38a for exchanging signals with the outside, a ROM 38b for storing programs, etc., a RAM 38c for storing various data, and various arithmetic operations. Comprising a CPU 38D. 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, respectively. 4 2 and 4 4 are for supplying a microcomputer 38 with 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, respectively. Things.

Reference numeral 48 denotes a display panel mainly including the organic EL element of the present invention, which is connected to a 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 a plurality of transistors that are individually connected to the vertical electrode row of the display panel 48. Comprising. 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 the horizontal electrode row of the display panel 48. When one of the transistors in the driver circuit 46 is turned on, the driver circuit 46 is turned on. Horizontal electrodes connected to transistors The column will be grounded.

Since the information display device of this example is configured as described above, when the transistors in the driver circuits 36 and 46 are turned on according to the instruction of the microcomputer 38, the display panel 48 in the vertical and horizontal directions is turned on. A predetermined voltage is applied between the corresponding electrode rows, 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 that electrode row. When the selected transistors are sequentially turned on, the 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, since the driver circuit 36 in this example has data registers for the electrode rows, it is preferable to drive the transistors based on the stored data.

The information to be displayed is supplied from the outside in accordance with the display speed and cycle, or the information is stored in the ROM 38b in advance for information having a fixed pattern such as character information. This may be used as data. In addition, when displaying a normal NTSC television broadcast, first, a received signal is separated into a horizontal synchronization signal and a vertical synchronization signal according to a horizontal frequency and a vertical frequency based on a broadcasting standard, and a video signal is also displayed. The signal is converted to a digital signal corresponding to the number of pixels on the display panel 48. By supplying these signals to the microcomputer 38 in synchronization with each other as appropriate, a television broadcast can be displayed on the display panel 48. Industrial applicability As described above, the present invention is based on the discovery of a novel industrially useful property of a coumarin derivative having a chalcone-like structure in a molecule. The coumarin derivative used in the present invention has an emission maximum in the visible region, particularly in the red region or near-red region, and forms a stable thin film in a glassy state, and thus is extremely useful as a luminescent agent for organic EL devices. . Since the organic EL device of the present invention using such a luminescent agent is excellent in luminous efficiency and durability, it can be used in combination with or without a filter for blocking light having a wavelength of 585 nm or less. As a light source that emits orange light or white light, it can be extremely advantageously used in a light-emitting body in general lighting and in a wide variety of information display devices that visually display information such as image information and character information.

It can be said that this invention having such remarkable functions and effects is a significant invention that greatly contributes to the art.

Claims

The scope of the claims

1. Coumarin derivative represented by general formula 1, general formula 1:

—In the general formula 1, to R ₆ and R _{a to} R ₁₂ are a hydrogen atom or a suitable substituent, and R ₇ is a hydrogen atom. When one of R ₂ and is a substituent represented by the general formula 2, the other represents a hydrogen atom or another substituent other than the substituent represented by the general formula 2.

General formula 2:

Ria

―

\

In R1 the general formula 2, 1¾ _{1 3} and _{1 4} are each independently either hydrogen atom, or an aliphatic hydrocarbon group, an aromatic hydrocarbon group or ether group, and these aliphatic hydrocarbon radicals, aromatic The group hydrocarbon group and the ether group may have a substituent.

2. In the general formula 1, any one of R ₂ or R,, is a substituent represented by the general formula 2, and in the R ₂ or R,, R ₁₃ and / or R in the general formula 2 _{1 4,} respectively, R ₂ or R, carbon atoms you adjacent to the carbon atom is attached a cyclic structure Z, and / or Z ₂ or, alternatively, by forming a Z ₃ and / or Z _4, generally 2. The coumarin derivative according to claim 1 represented by either formula 3 or formula 4.

3 -. Corresponding to general formula 1 R, to the compound represented by Formula 5 and, represented by the formula of engagement by the formula 6 having 1 to R ₈ or R, ₂ corresponds to having R ₆ 3. The method for producing a coumarin derivative according to claim 1, wherein the method comprises reacting the coumarin derivative with a product.

General formula 5:

-General formula 6

4. A luminescent agent for an organic electroluminescent device, comprising a coumarin derivative represented by the general formula 1. General formula 1:

In the general formula 1, R 1 to R ₂ represent a hydrogen atom or a substituent of an appropriate substituent.

5. —R ₂ and / or in the general formula 1 is a substituent represented by the general formula 2, and R ₂ , R ₃ and / or R _H in the general formula 2 A carbon atom adjacent to the carbon atom to which ₂ is bonded, or a carbon atom adjacent to the carbon atom to which R _n is bonded, forming a cyclic structure Z, Z ₂ , Z ₃ and / or Z ₄ The luminescent agent for an organic electroluminescent device according to claim 4, wherein the luminescent agent is represented by the following general formula 5.

General formula 2:

Rl3

-N

Rl4

In the general formula 2, R „and R and ₄ each independently represent a hydrogen atom or an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an ether group, and these aliphatic hydrocarbon groups and aromatic groups The hydrocarbon group and the ether group may have a substituent.

6. The organic electroluminescent device according to claim 4 or 5, comprising, together with the coumarin derivative represented by the general formula 1, one or more other luminescent compounds. Luminescent agent for field light emitting devices.

7. The luminescent agent for an organic electroluminescent device according to claim 6, wherein the other luminescent compound is a quinolinol metal complex.

8. The luminescent agent for an organic electroluminescent device according to claim 4, wherein the luminescent agent has an emission maximum in a red or near red region.

9. Claims 4, 5 and 5 comprising a coumarin derivative represented by the general formula 1 and one or more other luminescent compounds having an emission maximum in the blue or green region. Item 9. The luminescent agent for an organic electroluminescent device according to Item 6, 7 or 8.

10. The claim 4 comprising, together with the coumarin derivative represented by the general formula 1, one or more other light-emitting compounds having a fluorescence maximum at a wavelength of 43 to 50 nm. A luminescent agent for an organic electroluminescent device according to any one of Items 5, 6, 7, 8, and 9.

11. An organic electric field using the luminescent agent for an organic electroluminescent element according to claim 4, 4, 5, 6, 7, 8, 9, or 10. Light emitting element.

12. A structure having a hole injection / transport layer and / or an electron injection / transport layer, if necessary, together with an anode, a light-emitting layer and a cathode. The organic electric field according to claim 11, comprising the luminescent agent for an organic electroluminescent element according to claim 5, 6, 7, 8, 9, or 10. Light emitting element.

13. The organic electroluminescent device according to claim 11 or 12, which emits light in a red or near red region.

14. The organic electroluminescence according to claim 11, 12, or 13, wherein the light emission is red light by combining a filter that blocks light having a wavelength of 585 nm or less. element.

15 5. The luminescent layer contains one or more other luminescent compounds having a luminescent maximum in the blue or green region together with the coumarin derivative represented by the general formula 1 to emit light with white light. 14. The organic electroluminescent device according to claim 11, 12 or 13, wherein

16. The organic electroluminescent device according to claim 15, wherein the other luminescent compound has a fluorescence maximum at a wavelength of 43 to 51 nm.

17. A display panel using the organic electroluminescent element according to claim 11, 11, 12, 13, 14, 15, or 16.

18. An information display device using the organic electroluminescent device according to any one of claims 11, 12, 13, 13, 14, 15, and 16.