WO2007046247A1 - Compose luminescent de type rouge nil emettant une lumiere rouge, element luminescent et plastique moule - Google Patents

Compose luminescent de type rouge nil emettant une lumiere rouge, element luminescent et plastique moule Download PDF

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Publication number
WO2007046247A1
WO2007046247A1 PCT/JP2006/319995 JP2006319995W WO2007046247A1 WO 2007046247 A1 WO2007046247 A1 WO 2007046247A1 JP 2006319995 W JP2006319995 W JP 2006319995W WO 2007046247 A1 WO2007046247 A1 WO 2007046247A1
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WO
WIPO (PCT)
Prior art keywords
light
light emitting
red
layer
molded body
Prior art date
Application number
PCT/JP2006/319995
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English (en)
Japanese (ja)
Inventor
Tadao Nakaya
Akio Tajima
Tomoyuki Saikawa
Original Assignee
Hirose Engineering Co., Ltd.
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Publication date
Application filed by Hirose Engineering Co., Ltd. filed Critical Hirose Engineering Co., Ltd.
Publication of WO2007046247A1 publication Critical patent/WO2007046247A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen

Definitions

  • the present invention relates to a Nile red red light emitting compound, a light emitting element, and a plastic molded body. More specifically, the present invention relates to a Nile red red light emitting capable of emitting red light close to crimson with high brightness when electric energy is applied. The present invention relates to a compound, a light emitting element, and a plastic molded body that emits light upon irradiation with ultraviolet rays or the like.
  • organic electroluminescent devices also referred to as organic electroluminescent devices or organic EL devices.
  • Patent Document 1 As an organic compound capable of emitting red light, a Nile red-based red light emitting compound can be given (Patent Document 1).
  • Patent Document 1 Pamphlet of International Publication No. 03/062213
  • An object of the present invention is a Nile red red light emitting compound, which is capable of emitting red light close to crimson with high brightness when electric energy is applied, close to crimson! ⁇
  • a light emitting element that emits red light with high luminance and a plastic molded body that can emit light by irradiation with ultraviolet rays or the like.
  • Claim 1 is a Nile red red light-emitting compound characterized by having a structure represented by the following formula (1) or formula (1A):
  • R 1 represents a hydrogen atom or an alkyl group.
  • R 2 represents a hydrogen atom or an alkyl group.
  • Claim 2 is a plastic molded article formed by molding a resin composition containing the Nile red red light emitting compound according to Claim 1 and a plastic
  • Claim 3 is a pair of plastics.
  • a light emitting element comprising a light emitting layer containing the Nile red-based red light emitting compound according to claim 1 provided between the electrodes.
  • the Nile red-based red light-emitting compound represented by the formula (1) or the formula (1A) has a high-luminance red light emission due to substitution of an electron-withdrawing —CN group on the anthracene skeleton or pyrene skeleton. Is possible. Since this Nile red red light emitting compound has a melting point exceeding 330 ° C., it does not decompose even if it is mixed with a general-purpose synthetic resin and molded.
  • the Nile red red light emitting compound according to the present invention and a general-purpose synthetic resin such as talyl resin, methacrylic resin, polyolefin resin (especially amorphous polyolefin), polyester resin,
  • Various red light-emitting molded articles can be produced by molding a mixture or composition with polystyrene rosin or the like.
  • This red light-emitting molded article produces a plastic molded product capable of emitting red light with a bright red color with a light having a wavelength shorter than the emission peak of the Nile red-based red light-emitting compound, for example, blue LED light. .
  • the plastic molded body according to the present invention when the plastic as a matrix is a polar polymer, the red color emitted by the Nile red red light emitting compound of the present invention coexisting in the plastic molded body becomes deep.
  • a plastic molded body containing a polar polymer such as polyacrylo-tolyl, polyacrylamide, polybylpyrrolidone or the like as a matrix polymer or containing these and a Nile red-based red light emitting compound according to the present invention is not used.
  • the red color emitted from the plastic molded product becomes deeper.
  • the plastic molded body according to the present invention can take various forms depending on the plastic molding cage.
  • the plastic molded body may take a form in which light introduced from a part of the plastic molded body is formed so that a substantial overall surface force of the plastic molded body can be emitted.
  • the plastic molded body of the present invention can be used for keys in advertising lights, knocklights, display portions in mobile phones, key boards, mobile phones, numeric key boards, and the like.
  • the Nile red red light emitting compound according to the present invention can be used for a light emitting device having a light emitting layer containing the same. That is, the light emitting device according to the present invention has high brightness. Crimson red can be emitted. However, since the Nile red-based red light-emitting compound is robust, a light-emitting element having a light-emitting layer containing the Nile red-based red light-emitting compound can emit red light with a long lifetime.
  • FIG. 1 is an explanatory view showing an example of a plastic molded body of the present invention.
  • FIG. 2 is an explanatory view showing another example of the plastic molded body of the present invention.
  • FIG. 3 is an explanatory view showing another example of the plastic molded article of the present invention.
  • FIG. 4 is an explanatory view showing a light emitting device as an example according to the present invention.
  • FIG. 5 is an explanatory view showing a light emitting device as another example according to the present invention.
  • FIG. 6 is an explanatory view showing a light emitting device as another example according to the present invention.
  • FIG. 7 is an explanatory view showing a light emitting device as still another example according to the present invention.
  • FIG. 8 is a chart showing an NMR chart of iodinated Nile Red synthesized in Example 1.
  • FIG. 9 is a chart showing the NMR vector of the Nile red red light-emitting compound represented by the formula (7) synthesized in Example 1.
  • FIG. 10 is a chart showing the IR spectrum of the Nile red-based red light-emitting compound represented by the formula (7) synthesized in Example 1.
  • FIG. 11 is a spectrum diagram showing the fluorescence spectrum of the Nile red red light-emitting compound represented by the formula (7).
  • FIG. 12 is a chart showing the NMR vector of the Nile red-based red light-emitting compound represented by the formula (9) synthesized in Example 2.
  • FIG. 13 is a chart showing an IR spectrum of a Nile red-based red light-emitting compound represented by the formula (9) synthesized in Example 2.
  • FIG. 14 is an explanatory view showing a light emitting device as an example.
  • Nile red red light-emitting compound according to the present invention basically has a structure represented by the following formula (1) or formula (1A).
  • R 1 is a hydrogen atom or an alkyl group, preferably a lower alkyl group having 1 to 5 carbon atoms.
  • Examples of the lower alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
  • R 2 is a hydrogen atom or an alkyl group, preferably a lower alkyl group having 1 to 5 carbon atoms. It is.
  • the lower alkyl group represented by R 2 is the same as in the case of R 1 .
  • R 1 and R 2 may be the same lower alkyl group or different lower alkyl groups.
  • suitable —NR 2 is a jetyl amino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino. Group, di-s-ptylamino group, di-t-pylamino group and the like.
  • Nile red red light emitting compound represented by the formula (1) can be produced as follows.
  • a Nile red compound is reacted with iodine as an example of a halogenating agent.
  • iodine as an example of a halogenating agent.
  • pyridine can be used as the solvent, and the reaction temperature can include, for example, 60 to 75 ° C.
  • halogenating agent other than iodine a general halogenating agent capable of substituting hydrogen on the aromatic ring with a neurogen can be used.
  • halogenating agent include sulfuryl chloride and phosphorus pentachloride when hydrogen on the aromatic ring is substituted with chlorine.
  • N-halosuccinimide such as N-bromosuccinimide
  • halomalonic acid dialkyl such as dialkyl bromomalonate
  • the Nile red compound as a raw material in the formula (2) and the halogenating agent other than iodine easily react by heating in a solvent.
  • the solvent include acetic anhydride, acetic acid, an acid anhydride having 5 or less carbon atoms, benzene, and toluene in addition to the above pyridine.
  • Aromatic solvents such as benzene, dioxane and the like can be used.
  • the reaction temperature is usually 100 to 250 ° C, preferably 100 to 170 ° C.
  • the desired halogenated Nile Red compound can be obtained by performing a refining operation and a separation operation according to a conventional method.
  • the Nile red red light-emitting compound represented by the formula (1A) is also an iodide and 1 Promo 6 cyanopylene represented by the formula (2). It can manufacture by making it react.
  • a plastic molded body according to one aspect of the present invention is formed by molding a resin composition containing plastic and the Nile red red light emitting compound according to the present invention.
  • a molded body that is formed so that light is introduced from a part of the plastic molded body and the other partial light of the plastic molded body can be emitted.
  • a molded body formed so that light introduced from a part of the plastic molded body can be emitted from the substantially whole surface of the plastic molded body can be mentioned.
  • a plastic molded body 1 shown in FIG. 1 is a solid body having an oval main body 2 and a light introducing portion 3 that is partially narrowed so that the diameter gradually decreases.
  • the main body 2 is solidly formed of the light emitting compound according to the present invention and a plastic containing the light emitting compound.
  • the plastic molded body 1 contains the luminescent compound in the present invention.
  • a light source portion 4 having an LED is attached to the light introducing portion 3 in the plastic molded body 1. In the optical product composed of the light source unit 4 and the plastic molded body 1, the light that also generates the LED force in the light source unit 4 is introduced from the light introducing unit 3 into the solid body.
  • the light introduced into the solid body diffuses in the egg-shaped main body 2 to excite the light-emitting compound contained in the main body 2, and the excited light-emitting compound emits light. Emanates from the entire surface.
  • the plastic molded body 1 When the plastic molded body 1 is viewed from the outside, light emitted from the light emitting compound excited by the energy of light emitted from the single LED mounted in the light introduction 3 as a point light source is emitted from a plurality of light source powers. The entire plastic molded body 1 appears to emit light as if it were light.
  • the plastic molded body 1 shown in FIG. 1 diffuses the light introduced by the LED point light source by the action of the lens, and emits red light with a wide light emitting area.
  • the plastic molded body 1 shown in Fig. 1 is, for example, a guide light arranged on a runway to ensure the safety of airplane takeoff and landing at night, night indicator lights on roads, and tunnels. It can be used for internal lighting.
  • the shape of the plastic molded body 1 shown in FIG. 1 is not particularly limited, and can be variously modified depending on the application.
  • the plastic molded body 1 can be, for example, an emblem, an advertisement display, an illumination display, or the like.
  • shapes other than the shape of the plastic molded body 1 shown in FIG. 1 include, for example, a disk shape, a columnar shape, a polygonal shape such as a flat or long rectangular column shape, a ring shape, a football shape, a spherical shape, a pear shape, Various shapes such as lenticular and broad bean can be raised.
  • the plastic molded body 1 shown in FIG. 1 is a quadrangular pyramid
  • the plastic molded body 1 can be used for a key in a keyboard.
  • plastic If the LED on the bottom of the form 1 is equipped with an LED, the entire key board can emit light, and a colorful or light-emitting key board can be realized.
  • the plastic molded body 1 can also contain minute bubbles inside. When bubbles are contained in the plastic molded body, the plastic molded body 1 scatters the light generated by the light-emitting compound excited by the light emitted from the light source such as LED, and further scatters with fine bubbles. In addition, light of a color corresponding to the light emitting compound is illuminated from the entire plastic molded body 1 by total reflection at the bubble interface.
  • the plastic molded body 1 can be made into an emblem, an advertising display, a lighting display, etc. also by including bubbles in this way.
  • the plastic molded body 1 may contain a filler such as fine beads or a light diffusing material.
  • a filler such as fine beads or a light diffusing material.
  • the same effect as the microbubbles can be obtained.
  • the particle size of the microbeads is made small, for example, if the particle size of the microbeads is made nano-order, light is diffused by the light diffusion effect of such microbeads. Uniform light emission that gives a soft impression is obtained because the microbeads dispersed in the plastic molding are not visible.
  • a plastic molded body 1A shown in FIG. 2 is a transparent plastic or glass convex lens portion 5B attached to a large-diameter opening 5A in a cylindrical body 5 having a substantially frustoconical side surface portion.
  • the light guide is mounted on the small-diameter opening 5C in the cylindrical body 5 so as to face each other.
  • a surface of the light guide portion facing the convex lens portion 5B has a cut surface 5D having various shapes for diffusing light, such as radial streaks and diamond cuts.
  • the plastic molded body 1A as the light guide portion contains the light emitting compound in the present invention.
  • a light source unit 4 having an LED is mounted on the surface of the plastic molded body 1A opposite to the cut surface 5D.
  • the plastic molded body 1A, the side surface portion 5, the convex lens portion 5B, and the light source portion 4 form an illumination device 6. It should be noted that in this illumination device 6, the light source of the light irradiated outside the convex lens portion 5B force is not an LED. In various devices that use plastic moldings, such as lighting devices 6, LEDs are light-emitting substances contained in plastic moldings. Acts as an energy source to excite quality. Therefore, in the lighting device 6 shown in FIG. 2 and the lighting device having the second plastic molded body described later, this plastic molded body serves as a light source.
  • the lighting device 6 when light emitted from the LED power in the light source unit 4 is incident on the plastic molded body 1A, the Nile red red light emitting compound contained in the plastic molded body 1A is excited. As a result, a crimson red color is produced with high brightness.
  • the light emitted in the plastic molded body 1A is diffused and emitted from the cut surface 5D, and the light diffused and advanced in the cylindrical body 5 is further magnified and emitted by the convex lens portion 5B.
  • the lighting device 6 can be used, for example, as a warning light, a night light, and a brake lamp of an automobile.
  • a single plastic molded body 1A is disposed.
  • the number of plastic molded bodies 1A disposed may be plural.
  • a second plastic molded body is disposed between the plastic molded body 1A and the convex lens portion 5B in the vicinity of the plastic molded body 1A. It's okay.
  • a diamond cut surface is formed in the same manner as in the plastic molding 1A.
  • the second plastic molded body is disposed in the cylinder 5 so as to isolate the space in the cylinder 5 into two, and the diamond-cut surface faces the convex lens portion 5B. As described above, when the two plastic molded bodies are arranged in the lighting device 6, more uniform light can be generated.
  • a plastic molded body 1B shown in FIG. 3 includes a light guide portion 7A formed in an elongated shape and a light guide portion 7B formed on one peripheral surface of the light guide portion.
  • the entire light guide 7A is formed solid.
  • This plastic molded body 1B contains the luminescent compound in the present invention.
  • the light guide 7B is diamond cut. Further, a light source unit 4 having an LED is attached to the other end of the light guide unit 7A.
  • the light guide optical device 7 is formed by the rear portion 7 A and the light source portion 4.
  • the light guide optical device 7 when the light emitted from the LED force in the light source section 4 is incident on the plastic molded body 1B, the light emitting compound contained in the plastic molded body 1B is excited, and then Luminescence specific to the luminescent compound occurs. 1B plastic molded body The light emitted from the light guide 7A repeats irregular reflection at the interface within the light guide 7A, travels through the light guide 7A, reaches one end of the light guide 7A, and goes outside through the light derivation 7B. Light is fired. In this case, the red light characteristic of the Nile red red light emitting compound that has reached the light deriving unit 7B is radiated to the outside from the light deriving unit 7B that has been cut.
  • the light guide 7A which is the plastic molded body 1B
  • the light guide 7A can be bent with an arbitrary curvature. Further, the length of the light guide portion 7A can be arbitrarily determined according to the application. Therefore, the light guide optical device 7 provided with the light guide portion 7A can be applied to various uses based on its function.
  • the light guide optical device 7 is an internal view. It can be used for a light guide member in a mirror, an in-road lighting device that illuminates by being inserted into the in-road.
  • plastic molded body shown in FIG. 3 shows an example, and it goes without saying that various long shapes not shown in FIG. 3 can be adopted.
  • various shapes such as a triangle, a square, a flat quadrangle, and an ellipse can be taken.
  • the plastic molded body shown in FIG. 3 can also contain a filler or a diffusion material such as microbubbles or microbeads.
  • a lens attached to a strobe light emitting hole in a digital camera equipped in a mobile phone, and a strobe light emitting hole in a digital camera for example, a lens attached to a strobe light emitting hole in a digital camera equipped in a mobile phone, and a strobe light emitting hole in a digital camera.
  • worn can be mentioned.
  • FIG. 4 is an explanatory diagram showing a cross-sectional structure of a light-emitting element that is also a single-layer organic EL element.
  • the light-emitting element A includes a light-emitting layer 13 and an electrode layer 14 containing a Nile red-based red light-emitting compound according to the present invention on a substrate 11 on which a transparent electrode 12 is formed. It consists of
  • the light-emitting element A shown in FIG. 4 includes a transparent electrode when the light-emitting layer 13 contains the Nile red red light-emitting compound, blue light-emitting compound, and green light-emitting compound according to the present invention in a balanced manner. When a current is passed through 12 and electrode layer 14, it emits white light.
  • the Nile red-based red according to the present invention is contained in the light-emitting layer 13 in order to emit white light.
  • the total content of each of the light-emitting compound, the blue light-emitting compound, and the green light-emitting compound and the ratio of each content differ depending on the type of each light-emitting compound, and specifically, appropriately determined according to the type of each light-emitting compound. Is done.
  • the light-emitting layer 13 may contain the Nile red red light-emitting compound according to the present invention.
  • the light emitting element is intended to emit light of any color other than white and red
  • all of the Nile red red light emitting compound, the blue light emitting compound, and the green light emitting compound according to the present invention are used. It is good to change content and each content ratio suitably.
  • the mixing ratio of the Nile red red light emitting compound, the blue light emitting compound and the green light emitting compound in the light emitting layer is usually 5 to 200 by mass ratio. : 10 to 100: 50 to 20000, preferred ⁇ is 10 to: LOO: 50 to 500: 100 to 10000.
  • blue light-emitting compound examples include diphenyl bibiphenol-based blue light-emitting compound, stilbene-based blue light-emitting compound, and the like.
  • suitable diphenylbirubinol blue light emitting compounds include DPVBi represented by the formula (4).
  • green light emitting compound examples include a coumarin green light emitting compound, an indophenol green light emitting compound, and an indigo green light emitting compound, which are represented by the formula (5).
  • a coumarin green light emitting compound is preferred.
  • the light emitting element A shown in FIG. 4 has a large planar shape as a whole
  • the light emitting element A is mounted on, for example, a wall surface or a ceiling to provide a large area wall surface white light emitting element and a large area ceiling surface white light emitting element.
  • the light emitting element can be used as a surface light source in place of a conventional linear light source such as a fluorescent lamp or a point light source such as a light bulb.
  • wall surfaces, ceiling surfaces, or floor surfaces of residential rooms, office rooms, vehicle interiors, and the like can be illuminated or illuminated as a surface light source using the light emitting element according to the present invention.
  • the light-emitting element A can be used as a backlight for a display screen in a computer, a display screen in a mobile phone, a number display screen in a cash register, and the like.
  • the light-emitting element A can be used as various light sources such as direct illumination and indirect illumination, and can be lit at night and has good visibility, an advertising device, a road sign device, It can also be used for light sources such as light emitting bulletin boards and brake lamps in vehicles such as automobiles.
  • the light emitting element A since the light emitting element A has a red light emitting compound having a specific chemical structure in the light emitting layer 13, it has a long light emission lifetime. Therefore, the light emitting element A can be a light source that emits light with a long life.
  • the light-emitting layer 13 in the light-emitting element A includes the present invention.
  • the light emitting element A emits bright red with high luminance.
  • the light-emitting element A is a tubular light-emitting body in which a substrate 11 formed in a cylindrical shape, and a transparent electrode 12, a light-emitting layer 13, and an electrode layer 14 are laminated in this order on the inner surface side of the substrate 11. It can be. Since this light-emitting element A does not use mercury, it can be used as an environmentally friendly light source in place of a conventional fluorescent lamp using mercury.
  • the substrate 11 a known substrate can be adopted as long as the transparent electrode 12 can be formed on the surface thereof.
  • the substrate 11 include a glass substrate, a plastic sheet, ceramic, a metal plate formed by processing the surface to be insulative such as forming an insulating paint layer on the surface, and the like.
  • the light emitting element containing the blue light emitting compound, the green light emitting compound and the Nile red red light emitting compound according to the present invention in the light emitting layer 13 is opposite to the substrate 11.
  • This is a single-sided illumination device that can irradiate white light on the side.
  • the substrate 11 is transparent, it is a double-sided illumination device that can irradiate white light from the substrate 11 side and the opposite surface of the light emitting element.
  • the transparent electrode 12 employs various materials as long as it has a large work function and is transparent, and can act as an anode by applying a voltage to inject holes into the light emitting layer 13. can do.
  • the transparent electrode 12 is made of ITO, InO, SnO, ZnO.
  • inorganic transparent conductive materials such as compounds thereof, and conductive polymer materials such as polyaniline.
  • the transparent electrode 12 is formed on the substrate 11 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating, ion ion It can be formed by an assist vapor deposition method or other methods.
  • the electrode formed on the substrate does not have to be a transparent electrode.
  • the light emitting layer 13 contains the Nile red red light emitting compound according to the present invention when emitting red light, and when emitting white light, a blue light emitting compound or a green light emitting compound. And a layer containing the Nile red red light emitting compound according to the present invention.
  • the light-emitting layer 13 is a high-density layer in which the Nile red red light-emitting compound according to the present invention, or the Nile red red light-emitting compound, the green light-emitting compound, and the Nile red red light-emitting compound according to the present invention are dispersed in a polymer.
  • Nile red red light emitting compound according to the present invention or the blue light emitting compound, the green light emitting compound and the Nile red red light emitting compound according to the present invention are vapor-deposited on the transparent electrode 12. It can be formed as a deposited film.
  • Examples of the polymer in the polymer film include polybutcarbazole, poly (3-alkyl lentiophene), polyimide containing allylamine, polyfluorein, polyphenylene-butylene, poly-a-methylstyrene, biphenyl. -Lucarbazole Z ⁇ -methylstyrene copolymer and the like. Among these, polyburecarbazole is preferable.
  • the content of the Nile red red light emitting compound according to the present invention in the polymer film, or the total content of the blue light emitting compound, the green light emitting compound and the Nile red red light emitting compound according to the present invention is usually 0.01 to 2 mass%, preferably 0.05 to 0.5 mass%.
  • the thickness of the polymer film is usually 30 to 500 nm, preferably 100 to 300 nm. If the thickness of the polymer film is too thin, the amount of emitted light may be insufficient. If the thickness of the polymer film is too large, the driving voltage may become too high, which may be undesirable. Flexibility may be lacking when using a curved or annular body.
  • the polymer film comprises the polymer and the Nile red red light emitting compound according to the present invention, or the blue light emitting compound, the green light emitting compound, and the Nile red red light emitting compound according to the present invention in an appropriate solvent.
  • the film can be formed by a coating method such as spin casting, coating, or dipping.
  • the thickness of the vapor-deposited film is generally a force that varies depending on the layer structure in the light-emitting layer, etc. 0.1 to LOOnm.
  • the thickness of the deposited film is too small or too large, the same problem as described above may occur.
  • the electrode layer 14 is made of a material having a small work function, such as Mg, Ag, or aluminum. It can be formed of a simple metal or a metal alloy, such as an aluminum alloy or metallic calcium, or cesium carbonate.
  • the preferred electrode layer 14 is an alloy electrode of aluminum and a small amount of lithium, and a two-layer electrode that also has a cesium carbonate layer and an aluminum layer force.
  • the electrode layer 14 can be easily formed on the surface including the light emitting layer 13 formed on the substrate 11, for example, by a vapor deposition technique.
  • a buffer layer is interposed between the electrode layer 14 and the light emitting layer 13 regardless of which of the coating method and the vapor deposition method is used to form the light emitting layer.
  • Examples of the material capable of forming the buffer layer include alkali metal compounds such as lithium fluoride, alkaline earth metal compounds such as magnesium fluoride, oxides such as aluminum oxide, 4, 4, Biscarbazole biphenyl (Cz-TPD).
  • alkali metal compounds such as lithium fluoride
  • alkaline earth metal compounds such as magnesium fluoride
  • oxides such as aluminum oxide, 4, 4, Biscarbazole biphenyl (Cz-TPD).
  • m-MTDATA (4, 4 ,, 4 "-tris (3-methylphenol-aminoamine) ) Triphenylamine
  • phthalocyanine polyarine
  • polythiophene derivatives inorganic oxides such as molybdenum oxide, ruthenium oxide, vanadium oxide, and lithium fluoride.
  • FIG. 5 is an explanatory view showing a cross section of a multilayer organic EL element which is a light emitting element.
  • the light-emitting element B has a transparent electrode 12, a hole transport layer 15, light-emitting layers 13a and 13b, an electron transport layer 16 and an electrode layer 14 stacked in this order on the surface of the substrate 11. It becomes.
  • the substrate 11, the transparent electrode 12, and the electrode layer 14 are the same as those in the light-emitting element A shown in FIG.
  • the light emitting layer in the light emitting device B shown in FIG. 5 includes a light emitting layer 13a and a light emitting layer 13b, and the light emitting layer 13a is a deposited film formed by vapor deposition of a light emitting compound.
  • the light emitting layer 13b is a DPVBi layer. This DPVBi layer is a layer having a host material function.
  • the hole transport material contained in the hole transport layer 15 includes a triphenylamine compound such as N, N, -diferro-N, N, -di (m-tolyl) -benzidine (TPD), And And a-NPD, hydrazone compounds, stilbene compounds, heterocyclic compounds, ⁇ -electron starburst hole transport materials, and the like.
  • a triphenylamine compound such as N, N, -diferro-N, N, -di (m-tolyl) -benzidine (TPD), And And a-NPD, hydrazone compounds, stilbene compounds, heterocyclic compounds, ⁇ -electron starburst hole transport materials, and the like.
  • Examples of the electron transport material contained in the electron transport layer 16 include 2- (4-tert-butylphenol) -5- (4 biphenyl) -1, Examples include oxadiazole derivatives such as 3,4-oxoxadiazole, 2,5 bis (1 naphthyl) 1,3,4 oxaziazole, and 2,5 bis (5 'tert butyl-2'-benzoxazolyl) thiophene .
  • a metal complex material such as quinolinol aluminum complex (Alq3), benzoquinolinol beryllium complex (Bebq2) can be preferably used.
  • the electron transport layer 16 contains Alq3.
  • each layer is the same as that of a known multilayer organic EL element with conventional strength.
  • the light-emitting element B shown in FIG. 5 operates in the same manner as the light-emitting element A shown in FIG. 4, and emits light. Therefore, the light-emitting element B shown in FIG. 5 has the same application as the light-emitting element A shown in FIG.
  • FIG. 6 shows a third example of the light emitting device according to the present invention.
  • FIG. 6 is an explanatory view showing a cross section of a light-emitting element that is a multilayer organic EL element.
  • a light-emitting element C shown in FIG. 6 is formed by laminating a transparent electrode 12, a hole transport layer 15, a light-emitting layer 13, an electron transport layer 18 and an electrode layer 14 in this order on the surface of a substrate 11.
  • the light emitting element C shown in FIG. 6 is the same as the light emitting element B.
  • FIG. 7 shows another example of the light-emitting element.
  • the light emitting element D shown in FIG. 7 is formed by laminating a substrate 11, an electrode 2, a hole transport layer 15, a light emitting layer 13 and an electrode layer 14 in this order.
  • a hole transport layer containing a hole transport material is formed between a positive electrode that is a transparent electrode and a cathode that is an electrode layer formed on a substrate.
  • a two-layer organic low-molecular light-emitting device for example, a hole transport layer between an anode and a cathode, and a two-layer organic light-emitting layer containing a Nile red red light-emitting compound according to the present invention
  • a guest dye a two-layer dye-doped light emitting device comprising a light emitting layer containing a Nile red red light emitting compound and a host dye according to the present invention), and a hole transporting substance between the anode and the cathode.
  • a two-layer organic light-emitting device in which an electron-transporting light-emitting layer obtained by co-evaporation of an electron-transporting material is laminated (for example, a hole-transporting layer between an anode and a cathode, and this as a guest dye).
  • a two-layer dye-doped organic light-emitting device formed by laminating an electron transporting light-emitting layer containing a Nile red red light-emitting compound and a host dye according to the present invention), and between the anode and the cathode And a three-layer organic light emitting device comprising a layer transporting layer, a light emitting layer containing a Nile red red light emitting compound according to the present invention, and an electron transporting layer.
  • electron-transporting light-emitting layer in the light-emitting element usually, 50 to 80 wt% of poly Bulle force carbazole (PVK), and the electron transporting luminescent agent 5 to 40 mass 0/0, the present invention
  • PVK poly Bulle force carbazole
  • the electron transporting luminescent agent 5 to 40 mass 0/0 the present invention
  • the luminescent layer preferably contains rubrene as a sensitizer, and particularly contains rubrene and Alq3!
  • a red light emitting device using the Nile red red light emitting compound according to the present invention or a white light emitting device using the blue light emitting compound, the green light emitting compound and the Nile red red light emitting compound according to the present invention, for example, In general, it can be used as a DC-driven organic EL element, and it can also be used as a pulse-driven organic EL element and an AC-driven organic EL element.
  • the Et group represents an ethyl group.
  • Nile Red 10 g (31.4 mmol), Iodine 16 g (62.8 mm monole), and Pyridine 300 ml were added to a 500 ml three-necked flask, and the temperature was increased to 70 ° C with a high level of innorenos. Frozen, framed, and reacted for 4 hours. The reaction product was cooled to room temperature, added to 2000 ml of ice water, and the precipitated solid was filtered off with a glass filter. This solid was washed twice with 500 ml of 10% aqueous potassium iodide solution to remove excess iodine and dried under reduced pressure.
  • the dried product was purified by recrystallization from 1000 ml of toluene to obtain 9.Og of dark green crystals.
  • the NMR chart of this compound is shown in FIG. From the NMR chart shown in FIG. 8, this compound was identified as iodinated Nile Red.
  • a light emitting device 21 of the present invention shown in FIG. 14 was produced.
  • Each layer is as follows.
  • ITO 150nm thick ITO (Hole injection transport layer 24)
  • the hole injection layer is a layer into which holes (holes) are injected from the anode 23, and the hole transport layer is the same as the hole transport layer.
  • a 15 nm thick light emitting layer comprising 98% by mass of Alq3 and 2% by mass of the Nile red red light emitting compound represented by the above formula (7)
  • the electron injection layer is generally a layer into which electrons are injected from the cathode 28, and is a layer formed from, for example, a metal complex material.
  • Each of these layers was laminated by a vacuum vapor deposition method using a vacuum vapor deposition apparatus (Small-ELVESS011 type, manufactured by Totsuki Co., Ltd.).
  • the light emitting device 21 was used for light emission under the conditions shown in Table 1 below. The results are shown in Table 1.

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  • Organic Chemistry (AREA)
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  • Physics & Mathematics (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention porte sur un composé luminescent de type rouge Nil qui peut émettre une lumière de couleur rouge cardinal à une haute luminance, l'invention portant également sur un élément luminescent et sur un plastique moulé, chacun utilisant le composé. Le composé luminescent de type rouge Nil émettant une lumière rouge est caractérisé en ce qu'il a une structure représentée par la formule générale (1) ou la formule (1A). L'élément luminescent et le plastique moulé ont chacun une couche luminescente contenant le composé.
PCT/JP2006/319995 2005-10-18 2006-10-05 Compose luminescent de type rouge nil emettant une lumiere rouge, element luminescent et plastique moule WO2007046247A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007224171A (ja) * 2006-02-24 2007-09-06 Toray Ind Inc 発光素子材料および発光素子

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Publication number Priority date Publication date Assignee Title
JP2000080088A (ja) * 1998-06-26 2000-03-21 Fuji Photo Film Co Ltd エレクトロルミネツセンス素子及び環状アジン化合物
JP2000235892A (ja) * 1998-12-16 2000-08-29 Mitsubishi Chemicals Corp 有機電界発光素子
JP2001110570A (ja) * 1999-07-30 2001-04-20 Sony Corp 有機電界発光素子
JP2002134276A (ja) * 2000-10-30 2002-05-10 Sony Corp 有機電界発光素子
JP2003277369A (ja) * 2002-01-21 2003-10-02 Taiho Ind Co Ltd ナイルレッド系赤色発光化合物、その製造方法及びそれを利用した発光素子
WO2004067519A1 (fr) * 2003-01-31 2004-08-12 Hirose Engineering Co., Ltd. Compose electroluminescent rouge nil, procede de production d'un compose electroluminescent rouge nil et dispositif electroluminescent
WO2006101009A1 (fr) * 2005-03-18 2006-09-28 Hirose Engineering Co., Ltd. Compose luminescent rouge a base de rouge du nil et element luminescent l’utilisant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000080088A (ja) * 1998-06-26 2000-03-21 Fuji Photo Film Co Ltd エレクトロルミネツセンス素子及び環状アジン化合物
JP2000235892A (ja) * 1998-12-16 2000-08-29 Mitsubishi Chemicals Corp 有機電界発光素子
JP2001110570A (ja) * 1999-07-30 2001-04-20 Sony Corp 有機電界発光素子
JP2002134276A (ja) * 2000-10-30 2002-05-10 Sony Corp 有機電界発光素子
JP2003277369A (ja) * 2002-01-21 2003-10-02 Taiho Ind Co Ltd ナイルレッド系赤色発光化合物、その製造方法及びそれを利用した発光素子
WO2004067519A1 (fr) * 2003-01-31 2004-08-12 Hirose Engineering Co., Ltd. Compose electroluminescent rouge nil, procede de production d'un compose electroluminescent rouge nil et dispositif electroluminescent
WO2006101009A1 (fr) * 2005-03-18 2006-09-28 Hirose Engineering Co., Ltd. Compose luminescent rouge a base de rouge du nil et element luminescent l’utilisant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007224171A (ja) * 2006-02-24 2007-09-06 Toray Ind Inc 発光素子材料および発光素子

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