TW507002B - Organic electroluminescent device - Google Patents

Abstract

The object of the present invention provides an organic electroluminescent device having satisfactory luminous efficiency and durability and a satisfactory color purity, and uses thereof. The object is solved by providing an organic electroluminescent device comprising 4-cyanocoumarin derivative with a specific structure, luminophore using the derivative, and information displaying appliance, respectively.

Description

507002 A7 B7 V. Description of the invention (1) Technical field (please read the precautions on the back before filling out this page) The present invention relates to organic electric field light-emitting devices (hereinafter, referred to as "organic EL devices"). More specifically, This is an organic EL device containing a novel coumarin derivative. BACKGROUND OF THE INVENTION Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, which is described as the era of dataization, as much information as possible is displayed as accurately and quickly as possible, and the innovation requirements for data display components have not stopped. At present, in larger data display machines such as computer terminals and television receivers, Brownn tubes are mainly used, but because Brownn tubes are bulky, have large weight and high operating voltage, they are not suitable for people's livelihood. Use machines and small machines that value portability. Because small machines are thin and lightweight, flat, they must be made of materials with low operating voltage and low power consumption. Currently, liquid crystal elements are purchased for low operating voltage and low power consumption, and they are frequently used in many aspects. However, because the data display equipment using liquid crystal elements changes the contrast due to the viewing angle, it cannot be read at a certain angle and can not obtain a good display, and usually has a backlight, so it has the problem that the power consumption cannot be so small . The display elements that solve these problems are organic EL elements. Organic EL elements are usually inserted between a cathode and an anode with a thin film containing a luminescent agent, and a DC voltage is applied between the cathode and the anode. Holes and electrons are injected into the thin film respectively, and a luminescent agent is formed by recombination with each other. The light-emitting element emits light such as fluorescence and phosphorescence when the excited state is restored to the base state. Organic EL element This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 507002 A7 B7 V. Description of the invention (2) It is a light emitting device with a proper selection of the subject Agent, and changing the guest luminescent agent (blending agent) in which the host luminescent agent is combined, the characteristics of luminous hue can be appropriately changed. In addition, the combination of a host luminescent agent and a guest luminescent agent may significantly improve the luminous brightness and life. Because the organic EL element itself is a light-emitting element. Therefore, the data display device using such elements is not dependent on the viewing angle, and because it does not require a backlight, it has the advantage of reducing power consumption and can be called a light-emitting element with excellent principle. So far, although organic EL elements emitting light in the green region have been reported to improve the luminous efficiency through the combination of guest luminescent agents, no effective guest luminescent agent has been found in the light emitting in the red region, and it is still far from completely red. It has a long luminous life, and short durability, reliability is insufficient. For example, the organic EL elements disclosed in Japanese Patent Application Laid-Open No. 10-6 0 4 2 7 and U.S. Patent No. 4 7 6 9 2 9 2 have insufficient brightness, and because the light emission is not completely red, it is Achieving full color still has to be called still problematic. Furthermore, in the organic EL element supplied at low cost, the structure of the entire element can be simplified, or the deposition operation at the time of manufacture can not be achieved easily. The important point is to find a luminescent agent that does not require a guest luminescent agent in essence. . Regarding the luminescent agent used in the organic EL device, although various proposals have been made in the past, no compound that satisfies the above requirements has been found. In view of such a situation, an object of the present invention is to provide an organic EL device having excellent color purity of light emission in a visible region, particularly in a red region, and excellent light emission efficiency and durability, and an application thereof. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------: ---- 7 ^^ · Packing -------- Order ----- ---- (Please read the notes on the back before filling this page) 507002 A7 _ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (3) Disclosure of the invention In order to solve this problem, the inventors, etc. The person is committed to research, and the search results found that the third position has a hydrogen atom, a cyano group, a nitro group, a carboxyl group, an aryl group, a τπ group, an oxo group, a fluorenyl group or a polycyclic aromatic tobacco A valence group with a valence of 6 to 8 carbons and a series of 4 -cyanocoumarin derivatives composed of a 5-azanaphthalene ring (julolidine), which has a significant luminous ability in the visible light region, And it is extremely useful as a luminescent agent in organic EL elements. Furthermore, if an organic EL device containing such a coumarin derivative is applied with a DC voltage, it can efficiently emit light with excellent color purity, and it can be confirmed that it can last for a long time. The present invention is to create a novel coumarin derivative and find its industrially useful optical properties. Brief Description of the Drawings 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 of the present invention. Figure 3 is a block diagram of the data display machine according to the present invention (Description of Symbols 1, 10 2, 14 3, 16 4, 18 5 substrate cathode hole injection / transport layer light-emitting layer electron injection / transport layer This paper is applicable to China Standard (CNS) A4 specification (210 X 297 public love) ------- Ί II ^ — — — — — — — ^ »— — — — — 1— (Please read the notes on the back before filling This page) 5. Description of the invention (4) ◦ 20 anode 30 DC power supply 32, 34 booster circuit 36, 46 drive circuit 38 microcomputer 40 clock pulse generation circuit 42, 44 oscillating circuit 48 display panel is the best to implement the invention The organic EL device of the present invention contains a 4-cyanocoumarin derivative represented by Chemical Formula 1.

CN

X (Please read the notes on the back before filling out this page) The clothing is printed in Chemical Formula 1 by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and R i to R 4 each independently represent an alkyl group or an alkoxy group. The chain length at the base time is up to 3 carbons, and is usually selected from methyl and ethyl having 1 or 2 carbons. The alkoxy group is selected from the group consisting of 3 carbon atoms, and is usually a methoxy group and an ethoxy group having 1 or 2 carbon atoms. Moreover, in Chemical Formula 1, X is a hydrogen atom, a cyano group, a nitro group, a carboxyl group, an aryl group, an alkyl group, an alkoxy group, a heterocyclic group, or a polycyclic aromatic hydrocarbon. CNS) A4 specification (210 X 297 mm) 507002 A7 _ B7 V. Description of the invention (5) (Please read the notes on the back before filling this page) One kind of valence group, and this heterocyclic group may also have 1 Or plural substituents. Examples of each aryl group include phenyl, diphenyl, and triphenyl. The alkyl group is a methyl group or an ethyl group selected from 3 to 3 carbon atoms and usually 1 or 2 carbon atoms. The alkoxy group is a methoxy group and an ethoxy group selected from 3 to 3 carbon atoms and usually 1 or 2 carbon atoms. The heterocyclic group desirably contains one or more oxygen atom, sulfur atom, and / or nitrogen atom, and each heterocyclic group includes, for example, benzothiazolyl, naphthothiazolyl, benzoxazolyl, and benzimidazolyl. . Examples of the monovalent group of the polycyclic aromatic hydrocarbons include naphthyl, anthracenyl, and phenanthryl. Examples of the substituent of the heterocyclic group include alkoxy groups such as methoxy and ethoxy, and aryl groups such as phenyl, diphenyl, and triphenyl. Specific examples of the 4-cyanocoumarin derivative represented by Chemical Formula 1 include compounds represented by Chemical Formula 2 to Chemical Formula 10. Since these 4-cyanocoumarin derivatives have significant light-emitting ability in the visible region, they are extremely useful as host light-emitting agents in organic EL elements, and are blended in trace amounts in other host light-emitting agents to improve their performance. Guest luminous agent for luminous efficiency and luminescence spectrum. Chemical formula 2: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 507002 A7 B7 V. Description of the invention (6) Chemical formula 3:

OCH, chemical formula 4:

OCK

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Chemical Formula 5:

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -y-507002 A7 B7 V. Description of the invention (7) Chemical formula 6:

(Please read the precautions on the back before filling out this page) Chemical Formula 8: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

The size of this paper applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 507002 A7 __ B7 V. Description of the invention (8) Chemical formula 9:

Chemical formula 1 0:

(Please read the precautions on the back before filling out this page) Packing -------- Order ---- Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, 4-Cyanocoumarin Derivatives Used in the Invention Objects can be prepared in various ways. If economic importance is important, let the compounds represented by Chemical Formula 1 having R 1 to R 4 and X corresponding to Chemical Formula i be, for example, N, N -dimethylformamide, N, N -diethylethyl Hydrophilic solvents such as amidine, dimethylimine, N-methylpyrrolidone, and hexamethylphosphamide, or sodium cyanide and potassium cyanide in a mixture of these hydrophilic solvents and water It is preferable to perform a process of 4-cyanocyanation using a cyanide compound. The 4-cyanocoumarin derivatives shown in Chemical Formula 2 to Chemical Formula 10 can be easily prepared by this method. That is, the compound represented by the chemical formula 11 can be, for example, according to TK-II-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 507002 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs DESCRIPTION OF THE INVENTION (9) The method described in Hei 6 ~ 9 8 9 2 performs modulation. The 4-cyanocoumarin derivative thus obtained is usually used before, for example, liquid separation, tilting, filtration, extraction, concentration, thin-layer chromatography, column chromatography, gas chromatography, and local speed 'liquid chromatography. , Distillation, sublimation, crystallization, and the like are commonly used in the purification of similar compounds for purification, and if necessary, these methods are used in combination.

Many of the 4-cyanocoumarin derivatives shown in Chemical Formula 1 are in a long-wavelength visible light region starting at a wavelength of 600 nm, and in particular, an infrared region having a wavelength of 620 to 650 nm has a great light emission. Since a stable thin film is formed in a glass state, it is extremely useful as a light-emitting agent for organic EL elements. Organic EL elements that favorably use such coumarin derivatives are essentially EL elements that contain organic compounds with light-emitting capabilities. Generally, anodes with a positive voltage and cathodes with a negative voltage are set to regenerate holes and electrons. Single-layer and laminated organic ELs composed of a light-emitting layer that extracts light, a hole injection / transport layer that injects holes from the anode and transports, and an electron injection / transport layer that transports electrons from the cathode, as needed Components are important objects. In addition, the 4-cyanocoumarin derivative shown in Chemical Formula 1 can be used as a material for a hole injection / transport layer, a material for an electron injection / transport layer, and a micro-paper scale in other host luminescent agents. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) Participant · Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative, printed 507002 A7 _________ B7 V. Invention Description ( 10) The amount of guest luminescent agent that is blended and used to improve its luminous efficiency and luminescent spectrum. Therefore, in organic EL elements that use one or more of these materials as an indispensable element, they can be used alone or with other luminescent agents. The combination of the material for the hole injection / transport layer and / or the material for the electron injection / transport layer can be used very advantageously. Alas, in the case of the laminated organic EL device, in the case where the light emitting agent has both hole injection / transport capability and electron injection / transport capability, the hole injection / transport layer or electron injection / transport layer can be omitted, respectively, and, In a case where one of the material for the hole injection / transport layer and the material for the electron injection layer has the other function, the electron injection / transport layer or the hole injection / transport layer may be omitted, respectively. The organic EL device of the present invention is composed of a single layer type and a laminated type as described above. The operation of an organic EL device is essentially a process of injecting electrons and holes from an electrode. The process of electrons and holes moving in a solid, the process of recombination of electrons and holes to generate a singlet or triplet exciton, and the process of emitting light from this exciton are composed of single-layer organic EL elements and In the laminated organic EL device, there is essentially no difference. However, in the single-layer organic EL device, the characteristics of the above four processes can be improved by only changing the molecular structure of the luminescent agent. In contrast, in the multilayer organic EL device, the functions required for each process are plural. Materials are shared, and each material can be independent and optimized. Therefore, in general, the laminated structure is easier to achieve the desired performance than the single-layer structure. Therefore, regarding the organic EL element of the present invention, if a laminated organic EL element is used as an example, FIG. 1 is a schematic diagram of the laminated organic EL element of the present invention. In the figure, 1 is a substrate, usually using soda glass. The size of silicon paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) I ------ Ϊ 丨 丨 丨 Installation ----------- — — — — — i Aw (Please Read the precautions on the back before filling this page) 507002 A7 ----- B7 V. Description of the invention (11) (Please read the precautions on the back before filling this page) Glass of barium acid glass, aluminum silicate glass, etc. , Or plastic, ceramics and other general substrate materials. Desirable substrate materials are transparent glass, opaque ceramics such as plastic, and polystyrene, which are used in combination with transparent electrodes. 2 is the anode, usually through vacuum deposition, chemical deposition (CVD), sputtering, etc., 'closely adheres to the side of the substrate 1 and has a low electrical resistivity' and transmits light in the entire visible light region. Large conductive materials can be formed with a thickness of 10 to 100 nm. As the conductive material, metal oxides such as gold, platinum, nickel, tin oxide, indium oxide, a mixed system of tin oxide and indium oxide (hereinafter referred to as "IT0"), or aniline, thiophene, and pyrrole can be used. As a repeating unit of conductive oligomers and polymers. Among them, I T 0 has the characteristics that it can be easily obtained with low resistivity, and the use of acid etching can easily form a fine pattern. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as a hole injection / transport layer, usually in the same way as the anode 2 and tightly attached to the anode 2, for example, aromatic triamines, plutonium, carbazole or derivatives thereof The film can be formed to a thickness of 1 to 1,000 nm. The aromatic tertiary amine is, for example, N, -bis (3-methylphenyl) -N, -diphenyl (1,1 // biphenyl) -4,4 # monodiamine, N, N " Bis (1-naphthyl) -N, N-diphenyl (1,1 'biphenyl) -4,4-diamine (hereinafter referred to as "NPB") and triphenylamine and its polymers Those with a spiral center in the molecule, and so-called "π electron star burst molecules" such as triarylamine may also be used. 4 is a light-emitting layer, usually in the same way as the anode 2, is adhered to the hole injecting / transporting layer 3, and the luminescent agent is formed into a thickness of 10 to 1,000 nm, and desirably 10 to 200 nm Can be formed. Luminescent agent is thin -14-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) Chuan 7002 A7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (12) In the film state, a high fluorescence quantum yield is provided. For example, a 4-cyanocoumarin derivative represented by Chemical Formula 1 and Df thiazole, phenanthrene, triazole derivative, quinacridone, and rubrene can be used. Or a derivative thereof, or a quinoline derivative such as 8-hydroxyquinoline and a metal complex such as aluminum, zinc, beryllium or the like is used alone or in combination. In the case where a 4-cyanocoumarin derivative represented by Chemical Formula 1 is used as a guest luminescent agent, although it also varies depending on the type of the host luminescent agent used in combination, it is usually compounded with the host luminescent agent η & lt 〇. 〇1 mol% or more, preferably in the range of 0.1 to 10 mol%. 5 is an electron injecting / transporting layer, usually in the same manner as the anode 2, and is in close contact with the light-emitting layer 4, and is derived from the same compound in the light-emitting layer 4, or a cyclic ketone such as benzoquinone, anthraquinone, and fluorenone, or a derivative thereof Objects can be formed with a thickness of 10 to 500 nm. 6 is the cathode, usually in close contact with the electron injection / transport layer 5. It is a low electron injection / transport layer. The work function of the compound used in 5 (usually, 6 e V or less), such as lithium, magnesium, calcium, sodium, silver , Aluminum, indium and other metals are deposited alone or in combination, or a copper phthalocyanine buffer layer and an ITO electrode group are used to form an anode. The thickness of the cathode 6 is not particularly limited, and it can be set to a thickness of 100 nm or more in consideration of conductivity, manufacturing cost, thickness of the entire device, light transmittance, and the like. Alas, in order to improve the efficiency of electron injection, for example, an alkali metal or alkaline earth metal film may be provided between the electron injection / transport layer 5 and the cathode 6. In this way, the organic EL element of the present invention is formed on the substrate 1 by forming the anode 2, the cathode 6, the light-emitting layer 4, and the hole injection / transport layer 3 and the electron injection / transport layer 5 and the adjacent layers as needed in close contact with each other. All-in-one (please read the precautions on the back before filling out this page) Binding-ordering-i. This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm)-） & -Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 507002 A7 B7 V. Description of Invention (13). In the formation of each layer, in order to oxidize and decompose organic compounds, and to suppress the adsorption of oxygen and moisture to a minimum, it is desirable to operate under a high vacuum, in detail, below 10-5 Torr. In addition, when a host luminescent agent and a guest luminescent agent are used in combination to form a luminescent layer, the two luminescent agents are first mixed at a specified ratio, or the heating temperatures of the two luminescent agents are controlled independently of each other in vacuum deposition, and the luminescent layer can be adjusted. The ratio of two luminescent agents. Alas, the organic EL element constructed in this way must minimize deterioration in the use environment, and it is desirable to enclose a part or the whole of the element in an inert gas atmosphere with encapsulation glass and a metal cover, or with ultraviolet light. A protective film such as a hardened resin is covered. In the case of the organic EL element shown in FIG. 1, if a DC voltage is applied between the anode and the cathode, the holes injected by the anode 2 reach the light-emitting layer 4 through the hole injection / injection / transport layer 3, and The electrons injected by the cathode 6 pass through the electron in / transport layer 5 to the light emitting layer 4. As a result, in the light emitting layer 4, holes and electrons are recombined, and in the excited state of the luminescent agent, light having a predetermined wavelength is transmitted through the anode 2 and the substrate 1 and emitted. At this time, by coexisting the luminescence from both the host luminescent agent and the guest luminescent agent, white-based luminescence can also be obtained. If the purpose of the organic EL element of the present invention is explained, the organic EL element of the present invention may intermittently apply a higher voltage pulsed DC voltage based on the application, or a lower voltage non-pulsed DC voltage ( Usually, 3 to 10 V) is continuously applied. The organic EL element of the present invention has good luminous color purity in the visible light region, especially in the red region, and has excellent luminous efficiency and durability. Therefore, it is applicable to the Chinese National Standard (CNS) A4 specification for the luminous body and the paper size. (210 X 297 mm) ------- · ---- ^ · install -------- order --------- (Please read the notes on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 507002 A7 B7 V. Description of the Invention (14) There are various uses in the machine for displaying information. The organic EL element of the present invention as a light source has a small power consumption, and can be used as a light source for general lighting because it can form a lightweight flat plate. For example, it is used in liquid crystal elements, photocopying devices, and printing devices. , Electronic camera, computer and its application equipment, industrial control equipment, electronic measurement equipment, general measurement equipment, communication equipment, medical electronic measurement equipment, vehicle-mounted equipment such as automobiles, ship-mounted equipment, aircraft control equipment, The spacecraft is equipped with energy-saving and space-saving light sources in machinery, interior decoration, signage, and flags. When used in data display machines of computers, televisions, cameras, game consoles, clocks, oscilloscopes, radars, and sonars, it can be an organic EL element that emits light alone or in combination with red, green, or blue areas, as needed, such as After being processed into a display panel type, the conventional simple matrix method and active matrix method are used for driving. In the following, based on the implementation mode of the present invention, first, the preparation of 4-cyanocoumarin derivatives used in the present invention in Reference Examples 1 to 4 will be described, and the second embodiment will be described in connection with Examples 1 to 1. In Example 3, an organic EL element using the 4-cyanocoumarin derivative, a display panel using such an organic EL element, and a data display device using such a display panel. Reference Example 1: A 4-cyanocoumarin derivative is a formamidine compound represented by Chemical Formula 12 (9-formamidine-8) via a radical 1 '1,7,7-tetramethylbenzene- 5— 5 g of azanaphthalene ring and 1 · 7 g of cyanoacetamide were dissolved in methanol by heating and added to this paper. Applicable to China Paper Standard (CNS) A4 (210 X 297 mm): Bamboo_ "- ----- 1 · ---- Installation -------- Order --------- (Please read the precautions on the back before filling this page) 507002 A7 B7 V. Description of the invention (15) 0. 38 ml. The solution was cooled to room temperature after 3 hours of reaction under heating and reflux. 4 · 1 g of the sulfonium amine compound crystals shown in the chemical formula 13 precipitated were filtered, and 2.9 g of o-aminothiophenol and 10 ml of N, N-dimethylformamide were added respectively. After reacting at 110 ° C for 6 hours, the reaction was cooled to room temperature, and 30 ml of isopropyl ether was added. 4 · 1 g of the precipitated crystals were collected by filtration, and dissolved in 300 ml of acetone with heating, and half of the acetone was distilled off by filtration. The concentrated solution was cooled, and the precipitated crystals were re-filtered, washed with isopropyl ether, and dried to obtain 3.5 g of a compound crystal represented by Chemical Formula 14 bound to the benzothiazolyl group at the 3rd position. Chemical formula 1 2: Please read the back note Φ 14 first!

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Chemical Formula 3:

-18-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 507002 A7 B7 V. Description of the invention (16) Chemical formula 1 4:

(Please read the precautions on the back before filling in this page.) Packing ---- Order ---- Collect 2 · 3 grams of the compound of chemical formula 14 and disperse it in N, N -dimethylformamide In 33 ml, 30% (w / w) sodium cyanide aqueous solution 2.53 was added dropwise at room temperature, and after reacting for 1 hour, it was cooled to 0 to 10 ° C, and bromine was added dropwise. 4 4 ml, stir for 2 hours. The precipitated crystals were collected by filtration, washed with water and dried, and then purified by chromatographic column chromatography using chloroform as a developing agent to obtain brilliant green crystals of the 4-cyanocoumarin derivative represented by Chemical Formula 2 · 1 G. When printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs according to the conventional method, the melting point of the 4-cyanocoumarin derivative in this example is 2 6 to 2 6 9 ° C. If measured in dichloromethane, then It exhibits maximum absorption and maximum fluorescence at wavelengths of 5 6 4 nm and 6 1 4 nm, respectively. In addition, when 1 Η-nuclear magnetic resonance spectrum (hereinafter referred to as Γ1Η-NMR ") was measured in heavy chloroform, the chemical shift (5 (ppm, TMS) was 1.37 (6H, s), 1.59 (6H, s), 1.80 (2H, t), 1.85 (2H, t), 3.36 (2H, t), 3.45 (2H, t), this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 507002 A7 B7 V. Description of the invention (17) 7.39 to 7.44 (lH, m), 7.52 to 7.61 (lH, m), 7.72 (lH, s), 7.96 (1Η) , D) to 8 · 18 (1 Η, d) are observed at the peaks. Reference Example 2: 4-cyanocoumarin derivative In 19 g of amidonium compound shown in Chemical Formula 13 obtained by the method of Reference Example 1, 1-amino- 2 -naphthol was added separately 9.2 g And 50 ml of N, N-dimethylformamide, reacted at 110 ° C. for 4 hours, cooled to room temperature, and filtered the precipitated crystals. This crystal was dissolved in 60 ml of chloroform, filtered, and crystallized with 140 ml of methanol. The precipitated crystal was re-filtered and dried to obtain 18 · 2 g of a crystal of a compound represented by Chemical Formula 15. Chemical formula 1 5:.

5 g of the compound represented by Chemical Formula 15 was collected and dispersed in 50 ml of N, N-dimethylformamide, and a 30% (w / w) aqueous sodium cyanide solution was added dropwise at room temperature. 3 · 4 ml. After reacting for 1 hour, the reaction was cooled to 0 to 10 ° C, 0.59 ml of bromine was added dropwise, and stirred for 2 hours. 4 · 9g of the precipitated crystals were filtered, washed and dried, and the paper size was N. Applicable to China National Standard (CNS) A4 (210 X 297 mm)-------- i · pack- ------- Order --------- i. (Please read the notes on the back before filling this page) 507002 A7 B7 V. Description of the invention (18), N-dimethylformamidine The amine was recrystallized to obtain 2. 6 g of bright green crystals of a 4-cyanocoumarin derivative represented by Chemical Formula 5. C Please read the precautions on the back and fill in this page.] The melting point of the 4-cyanocoumarin derivative in this example is 3 2 2 to 3 2 6 ° C when measured by conventional methods. In the determination, the maximum absorption and the maximum fluorescence were shown at the wavelengths of 580 nm and 627 nm, respectively. In addition, when 1 Η-NMR was measured in heavy chloroform, the chemical shift 5 (?? 111, D ^ 18) was 1.40 (611,3), 1.60 (6H, s), 1.81 (2H, t), 1 · 87 (2Η, t), 3.36 (2H, t), 3.45 (2H, t), 7.58 to 7.63 (lH, m), 7.71 to 7.76 (lH, m), 7.79 (lH, s), 7.81 to Peaks were observed at 7.84 (111, 111), 7.94 to 7.99 (2H, m) and 9 · 01 (1Η, d). Reference Example 3: 4-Cyanocoumarin Derivatives Printed in the method of Reference Example 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed on the method shown in Chemical Formula 1 3 of the amidonium compound 3 · 4 g, and added 2 -3.0 g of amine-4 phenylthiophenol and 30 ml of N, N-dimethylformamide, after reacting at 140 ° C for 4 hours, cooling to room temperature, and filtering the precipitated crystals. This crystal was dissolved in 30 ml of chloroform, filtered, and 70 ml of methanol was added. The precipitated crystal was filtered again and dried to obtain 2.5 g of a crystal of the compound represented by Chemical Formula 1. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 507002 A7 _______B7 V. Description of the invention (19) Chemical formula 1 6:

(Please read the precautions on the reverse side before filling out this page) Collect 2.5 g of the compound shown in Chemical Formula 16 and disperse it in 5 ml of N, N-dimethylformamide, and drop it at room temperature. 1.6 ml of a 30% (w / w) aqueous sodium cyanide solution was added, and after reacting for 1 hour, the reaction was cooled to 0 to 10 ° C, and 3.1 ml of bromine was added dropwise, followed by stirring for 2 hours. The precipitated crystals were collected by filtration, washed with water and dried, and then purified by silica gel column chromatography using chloroform as a developing agent to obtain 1 · 9 g of bright green crystals of the 4-cyanocoumarin derivative shown in Chemical Formula 8. . When measured according to the usual method, the melting point of the 4-cyanocoumarin derivative in this example is 2 6 1 to 2 6 3 ° C. If measured in methylene chloride, the wavelengths are 5 6 9 nm and 6 1 7 nm shows the maximum absorption and the maximum fluorescence of the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, respectively. It is measured as 8. Medium} 1 y, S, chloro M}, and TS ，, ， m Η and ρ 6 op (δ R M Ν I Η s Η 6 / IV 8 3 Η 2 8 Η 5 2. (L〇, 8 Η to 2 6 (4 5 · 4 7 3), m), t Η J IX Η (2 1 (4 6 · 3 7 • to 3 6, 2). T 7 m Η 2 Γν IX 5 7 Η rH / (V 9 6 7 to 6 6 7 dd 5 7 7 to IX 7 7 1 ± ο 8m Η This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 507002 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) i Η, d) and 8 · 3 9 The peaks were observed at the positions (1 Η, d) respectively. Reference Example 4: 4 Monochlorosane derivative The sulfonium amine compound shown in Chemical Formula 13 obtained by the method of Reference Example 1 was used to collect 3.0 g of Add 2-amino-4,5-dimethoxy Sulfur: 3.0 and N'N-dimethylformamide 15 ml 'were reacted at 140 ° C for 4 hours, then cooled to room temperature, and the precipitated crystals were filtered. The crystals were dissolved in chloroform. A chloroform / ethyl acetate mixed solution was used as a developing agent and purified by silica gel column chromatography to obtain 2.5 g of a compound represented by Chemical Formula 17. Chemical Formula 17: 〇ch3

2.5 g of the compound represented by Chemical Formula 17 was collected and dispersed in 50 ml of N, N-dimethylformamide, and a 30% (w / w) aqueous sodium cyanide solution was added dropwise at room temperature. 2 · 0 liters. After reacting for 1 hour, the reactants are cooled to 0 ~ 10 ° C, 0. 25 ml of bromine is added dropwise, and stirred. 2 The size of this paper is applicable to Chinese National Standard (CNS) A4 (210 X 297 liters). (Li) -Zό-(Please read the notes on the back before filling out this page) Binding — Order II! 507002 Α7 Β7 V. Description of the invention (21) hours. The precipitated crystals were collected by filtration, washed with water and dried, and then purified by silica gel column chromatography using a chloroform / ethyl acetate mixture as a developing agent (please read the precautions on the back before filling this page). Shown as a brilliant green crystal of 4-cyanocoumarin derivative 1 · 1 g 0 The melting point of 4-cyanocoumarin derivative in this example is 3 0 8 to 3 1 2 ° C when measured according to a conventional method. If measured in dichloromethane, it shows maximum absorption and maximum fluorescence at the wavelengths of 5 7 6 and 6 2 9 nm, respectively. In addition, when 1Η-NMR was measured in dichloromethane, the chemical shift 5 (Ppm, TMS) was 1.32 (6Η, s), 1.60 (6H, s), 1.77 (2H, t), 1 83 (2Η, t), 3.29 (2H, t), 3.37 (2H, t) '3.98 (6H, s), 7.36 (1H, s), .49 (1H, s), and 7.61 (1H, Peaks were observed at positions s). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1 summarizes the physical properties of the 4-cyanocoumarin derivatives obtained by the methods of Reference Example 1 to Reference Example 4. In Table 1, the maximum absorption wavelength was measured by dissolving in methylene chloride. The maximum fluorescence wavelength was measured in dichloromethane at a concentration of 10-7 M. However, although the 4-cyanocoumarin derivative used in the present invention has some differences in raw materials, reaction conditions, and yield depending on the structure, it includes those shown in Chemical Formula 2 to Chemical Formula 10, and can be based on Reference Examples 1 to Reference Examples. The method described in 4 or can be easily modulated according to these methods. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 507002 A7 _B7 V. Description of the invention (22) Table 1: Compounds with maximum absorption wavelength and maximum fluorescence wavelength Melting point (° C) (nm) (nm) Chemical formula 2 564 614 266 to 269 Chemical formula 4 576 629 308 to 312 Chemical formula 5 580 627 322 to 326 Chemical formula 8 569 617 261 to 263 Example 1: Organic EL element will be aqua regia Patterned glass substrate with transparent IT 0 electrode at a thickness of 100 nm, ultrasonically cleaned with neutral detergent, pure water and isopropanol, and pulled up and dried from boiling isopropanol. It was washed with ultraviolet ozone and fixed in a deposition apparatus, and then decompressed at 10-7 Torr. Secondly, for a glass substrate having an I but transparent electrode surface as an anode, NP B was deposited to a thickness of 60 nm and a hole injection / transport layer was formed. Thereafter, while detecting with a film thickness sensor, any of the 4-cyanocoumarin derivatives shown in Chemical Formula 2, Chemical Formula 4, Chemical Formula 5, and Chemical Formula 8 obtained by the methods of Reference Examples 1 to 4 was used. It is co-deposited with tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as "A 1 q 3") at a weight ratio of 0 · 8: 100 to a thickness of 20 nm to form a light emitting layer. Furthermore, A1Q3 was deposited to a thickness of 40 nm, and after forming an electron injection / transport layer, lithium fluoride and aluminum were deposited in this order to a thickness of 0.5 nm and 150 nm, respectively, to form a cathode. After that, under the nitrogen atmosphere, the entire component was made of glass plate and UV-curable resin to this paper. The Chinese standard (CNS) A4 specification (210 X 297 mm) was applied. _ 心-------- · ---- Package -------- Order · ——----— (Please read the precautions on the back before filling this page) 507002 A7 B7 V. Description of the invention (23) Package, get 4 kinds of organic EL element. For the organic EL device obtained in this way, the light emission characteristics were tested in accordance with a conventional method. At the same time, except that the compound represented by Chemical Formula 18 is used in place of the 4-cyanocoumarin derivative, an organic EL element is prepared in the same manner as described above, and it is the same as that of the organic EL element using the 4-cyanocoumarin derivative. Handle the situation as a comparison. The results are shown in Table 2. Chemical formula 18: (Please read the precautions on the back before filling out this page) Packing -------- Order ---- Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs nm) Brightness (cd / m2) * 1 Lifetime (h〇 # 2 Remark Chemical formula 2 625 11 90 Inventive chemical formula 4 643 85 50 Inventive chemical formula 5 640 141 512 Inventive chemical formula 8 630 120 544 Inventive chemical formula 1 8 600 8 0 16 Control * 1: Measurement when driven with a current of 11 m A / cm 2 値 * 2: Half-life when driven with a constant current of 3 0 0 cd / m2 at constant current §.

-ZΌ-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 507002 A7 B7 V. Description of Invention (24) (Please read the precautions on the back before filling this page) The results shown in Table 2 As can be seen, if the organic EL element of this example is applied with a DC voltage, it will cause red light emission with great light emission in a visible light region exceeding a wavelength of 600 nm, especially in a wavelength of 620 to 650 nm. The light emission was confirmed at about 4V, and reached the highest brightness (6,000cd / m2) near 15V. The half-life of the brightness when driven with a constant current of 300 c d / m2 at a constant current was the same as that of the control group, or significantly exceeded that of the control group (over 100 hours). Part of the dark area (black spots) was not observed even after 100 hours from the start of light emission. In contrast, the organic EL device in the control group is as shown in the results of Table 2. The maximum emission wavelength is at a shorter wavelength (600 nm). If observed with the naked eye, the light emission is close to orange. These results indicate that the organic EL device of this example is a red light-emitting device with good color purity. Example 2: Display Panel Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The display panel shown in Figure 2 is a simple matrix display panel with the organic EL element of the present invention as the main body (20 electrode rows in the horizontal direction, vertical It is a 30-electrode column), and such a display panel is manufactured as follows. That is, first, on one side of the glass substrate 10 according to the method of Example 1, the anodes 14 are formed with I T 0 transparent electrodes, and then the anodes 14 are processed into strips by a wet etching method. Next, the hole injection / transport layer 16 and the light emitting layer 18 were sequentially formed according to the method of Example 1. After the cathode 20 was formed into a strip shape using a mechanical cover, a glass plate (not shown) and ultraviolet rays were formed. The hardening resin encapsulates the organic EL element.尙 On the display surface of this example, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 507002 A7

5. Description of the invention (25) In the plate, the temperature rise during use must be suppressed. If necessary, a heat radiation plate and a cooling fan can be installed on the back side of the cathode 200. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 3: Data display device Figure 3 shows a data display device using a display panel made in accordance with the method of Example 2. In FIG. 3, 30 is a DC power supply with an output voltage of 4.5 V, and two output circuits 32 and 34 are connected to its output end. The booster circuit 32 can supply a DC voltage in the range of 5 to 12 V, and the drive circuit 36 is connected to its output terminal. The other booster circuit 34 supplies a constant voltage of 5 V to the microcomputer 38. The microcomputer 38 is an I / 〇 interface 38a including external and transceiving signals, R.0M 38b for storing programs, R AM 38c for storing various data, and CPU 38d for performing various calculations. The microcomputer 38 is connected to the clock signal generating circuit 40, which supplies the 8 MHz clock signal to the microcomputer 38, and two oscillator circuits 4 2, 4 4, which are for the two The microcomputer 38 respectively supplies a signal for controlling the display speed from 5 to 50 Hz, and a signal for controlling the scanning cycle number from 0.2 to 2 κ Η z. 48 is a display panel with the organic EL element of the present invention as a main body, and is connected to a microcomputer 38 through a driving circuit 36, 46. The driving circuit 36 is a circuit for controlling a DC voltage from the booster circuit 32 to be applied to the display panel, and the display panel 48 includes a plurality of transistors each connected to a vertical electrode column. Therefore, 'if any of the transistors in this driving circuit 36 is turned on, the column of electrodes connected in the vertical direction of this transistor is out of order. (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 male f _ 28 507002 A7 B7) V. Description of the invention (26) (Please read the notes on the back first Please fill in this page again) Apply the voltage from the booster circuit 32. On the other hand, the drive circuit 4 6 is composed of a plurality of transistors individually connected to the display panel 48 horizontal electrode row. If any transistor is turned on, the electrode row connected to the horizontal direction of this transistor is grounded. Because the data of this example shows that the machine is so constructed, if the transistor in the drive circuit 36, 46 is turned on according to the instructions of the microcomputer 38, then The specified voltage is applied between the electrode columns corresponding to the vertical direction and the horizontal direction of the display panel 48 so that the organic EL element located at the intersection thereof emits light. Therefore, for example, a column is selected to appropriately control the horizontal direction of the driving circuit 46. Column, and this electrode column is grounded, and the transistors connected to the vertical direction electrode column of the appropriate control drive circuit 36 are sequentially turned on, then the entire horizontal electrode column can be scanned in the horizontal direction to display the _ The given pixels. If the scanning is repeated in the vertical direction in sequence, the entire screen can be displayed. Alas, the driving circuit 36 in this example is a data register with a row of electrodes, so it is suitable to be based on the memory. The data is driven by the transistor. The information printed and printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be supplied externally in accordance with the display speed and cycle, or, for example, textual data. M3 8 b can also memorize its pattern in advance and create it as data. In the case of displaying TV broadcasts in the usual NTSC mode, first, the received signal is based on the broadcast specifications, with the number of horizontal cycles and the number of vertical cycles. The signal is separated into a horizontal synchronization signal and a vertical synchronization signal, and the image signal is converted into a digital signal corresponding to 48 pixels of the display panel. These signals are appropriately supplied to the microcomputer 3 8 at the same time, and can be displayed on the display panel 4 8 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 507002 A7 B7__ V. Description of the invention (27) TV broadcast. Product availability As mentioned above, the present invention is based on the creation of novel 4-cyanocoumarin derivatives and the discovery of their industrially useful properties. Contains such 4-cyanocoumarin derivatives The organic EL element of the present invention has good luminous color purity in the visible light region, especially in the red region, and has excellent luminous efficiency and durability, so it is extremely beneficial to use as a luminous body as a general lighting source, and visual Various data display machines for displaying data. The invention which has achieved such a significant effect has contributed a lot to this field, and it can be said to be a significant invention. ------- · ---- Installation -------- Order ---------. 41 ^ (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau Staff Consumer Cooperatives Paper size applicable to Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

6. Application for Patent Scope No. 891 1 4372 Amended the scope of patent application (please read the precautions on the reverse side before filling out this page). May 91, Republic of China Amendment 1. An organic electric field light-emitting element containing 4-cyanocoumarin derivative represented by Chemical Formula 1: Chemical Formula 1: In Chemical Formula 1, 111 to 1 ^ 4 are each independently an alkyl group or an alkoxy group, and X is a hydrogen atom, a cyano group, a nitro group, a carboxyl group, an aryl group, an alkyl group, an alkoxy group, a heterocyclic group, or a polycyclic group. The aromatic hydrocarbon is a monovalent group, and the heterocyclic group may have a substituent. 2. The organic electric field light emitting device according to item 1 of the scope of patent application, which contains a 4-cyanocoumarin derivative represented by Chemical Formula 1 as a light emitting agent. · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. If the organic electric field light-emitting element of item 1 or 2 of the patent application scope, it has a great light emission in the visible light region exceeding the wavelength of 600 nm. 4. The organic electric field light emitting device according to item 1 or 2 of the patent application scope, which is a single-layer type or a multilayer type. 5. The organic electric field light emitting device according to item 1 or 2 of the scope of patent application, which has a maximum light emission in a visible light region exceeding a wavelength of 600 nm, and is a single-layer type or a multilayer type. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) ~ Γ: '507002 A8 B8 C8 D8 6. Application for patent scope 6. — A kind of light-emitting body, which is used as in patent application scope No. 1 or 2 $ The organic electric field light-emitting element. 7. A kind of light-emitting body, which uses the electro-mechanical field light-emitting element such as the third item in the scope of patent application. 8-A light emitting body, which uses a # machine electric field light emitting element such as the 4th in the scope of patent application. 9 · A light-emitting body using an organic electric field light-emitting element such as the item 5 in the scope of patent application. 10. If the organic electric field light-emitting element of the first or second item of the scope of patent application, it is used on the data display machine. 1 1 · If the organic electric field light emitting yak is No. 3 in the scope of patent application, ^ is used on data display equipment. 1 2. The organic electric field light-emitting element according to item 4 of the scope of patent application is used for data display equipment. 1 3 · The organic electric field light-emitting element such as item 5 of the scope of patent application is used in data display equipment. Packing --- c Please read the precautions on the back-fill out this page} Order · Home Country China Middle-size paper __I This printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs S N