CN107903898A - A kind of Lu2Zr2O7System phosphor and preparation method thereof - Google Patents

A kind of Lu2Zr2O7System phosphor and preparation method thereof Download PDF

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Publication number
CN107903898A
CN107903898A CN201711161443.9A CN201711161443A CN107903898A CN 107903898 A CN107903898 A CN 107903898A CN 201711161443 A CN201711161443 A CN 201711161443A CN 107903898 A CN107903898 A CN 107903898A
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doping
phosphor
acid
mms
ester
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CN201711161443.9A
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CN107903898B (en
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杨道救
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Tangshan Yelin Trading Co., Ltd
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Hangzhou Qingqing Science And Technology Co Ltd
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Priority to CN201810754680.4A priority Critical patent/CN109021965A/en
Priority to CN201810754681.9A priority patent/CN108912840A/en
Priority to CN201810754699.9A priority patent/CN108753295A/en
Priority to CN201711161443.9A priority patent/CN107903898B/en
Priority to CN201810754753.XA priority patent/CN108659839A/en
Application filed by Hangzhou Qingqing Science And Technology Co Ltd filed Critical Hangzhou Qingqing Science And Technology Co Ltd
Priority to CN201810754772.2A priority patent/CN108624321A/en
Priority to CN201810754723.9A priority patent/CN108690615A/en
Publication of CN107903898A publication Critical patent/CN107903898A/en
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    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/27—Lots, e.g. lottery tickets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like

Abstract

A kind of Lu2Zr2O7System phosphor, the molecular formula of the phosphor is Yb/Eu/Er:Gd2Ti2O7, the doping using the molar percent wherein doping of Yb as 10 ~ 30%, Eu is the doping of 1 ~ 10%, Er for 0.001 ~ 0.01%；The phosphor can obtain Er under 980nm shooting conditions3+Red emission is changed on the approximate simple spectrum band of ion, under 361nm, 393nm, 414nm, the excitation of 465nm xenon lamps, obtains Eu3+Lower conversion red emission.System of the present invention can realize conversion red emission up and down at the same time, and emission peak derives from different rare earth ions, with different spectrum shapes, and a variety of rare earth ions are simply blended in some common matrix systems, due to radiationless cross-relaxation probability larger between rare earth ion, it is difficult to realize that conversion shines up and down at the same time, thus the system that the present invention utilizes can be applied to antifalsification label material.

Description

A kind of Lu2Zr2O7System phosphor and preparation method thereof
Technical field
The invention belongs to phosphor field.
Background technology
Optical anti-counterfeiting label is that special fluorescent material is designed to pattern or word, is then led under external light source irradiation Cross naked eyes or special instrument is identified, wherein, the optical characteristics of fluorescent material determine that antifalsification label is imitated and replicates Complexity.Rare earth ion has abundant level structure, can realize shining for different colours, such as by being co-doped with Yb/ Er, under the conditions of 980nm laser excitations, can obtain Er3+Green emission, by being co-doped with Ce/Eu, under ultra violet lamp, It can obtain Eu3+Red emission.However, the common fluorescence feature of these rare earth ions is easy to be imitated, directly should be not easy For optical anti-counterfeiting label material.
The content of the invention
It is an object of the present invention to provide a kind of Lu2Zr2O7System phosphor, second object of the present invention It is to provide the preparation method of above-mentioned phosphor, phosphor of the invention can be in different-waveband shooting condition Under obtain having different spectrum shapes feux rouges realize it is false proof.
In order to realize first above-mentioned purpose, present invention employs following technical solution：
A kind of Lu2Zr2O7System phosphor, the molecular formula of the phosphor is Yb/Eu/Er: Gd2Ti2O7, with The doping that the doping that the molar percent wherein doping of Yb is 10 ~ 30%, Eu is 1 ~ 10%, Er is 0.001 ~ 0.01%； The phosphor can obtain Er under 980nm shooting conditions3+The upper conversion yellow emission of ion, in 365nm, 395nm is with the excitation of 420nm xenon lamps, obtaining Eu3+Lower conversion red emission.
Preferably, the doping using the molar percent wherein doping of Yb as 15 ~ 25%, Eu is mixing for 3 ~ 8%, Er Miscellaneous amount is 0.002 ~ 0.008%.As further preferably, using molar percent wherein doping of the doping of Yb as 18 ~ 22%, Eu Doping for 4 ~ 6%, Er is 0.004 ~ 0.006%.
In order to realize second above-mentioned purpose, present invention employs following technical solution：
A kind of preparation method for preparing the phosphor, this method comprise the following steps：
1）Will（10-25）% mMs of lutecium nitrate,（2-9）% mMs of ytterbium nitrate,（0.5-4）% mMs of europium nitrate,（0.2- 0.5）% mMs of erbium nitrate, with（20-30）% mMs of citric acid is added to（4-10）In milliliter ethanol, stir 30-60 minutes Obtain clear solution A；
2）Will（40-50）% mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；
3）By 2）In solution exist（40-60）DEG C insulation（1-2）Hour, untill xerogel is obtained；
4）By 3）Middle gained xerogel grinding（30-60）After minute, it is positioned in Muffle furnace, and（700-900）DEG C sintering（4- 8）Hour, obtain final product after furnace cooling.
The phosphor is applied to optical anti-counterfeiting label material.
The material of the invention can obtain shining for different colours under the shooting condition of different wave length.Bar is excited in 980nm Er can be obtained under part3+The upper conversion yellow emission of ion, under the excitation of 365nm, 395nm and 420nm xenon lamp, obtains Eu3+'s Lower conversion red emission.The characteristics of system, has：A, system can realize Eu under the excitation of the xenon lamp of different wave length3+Shine； B, system can realize that conversion shines up and down, and emission peak derives from different rare earth ions, has different glow colors at the same time With composing shape, and a variety of rare earth ions are simply blended in some common matrix systems, due to larger between rare earth ion Radiationless cross-relaxation probability, it is difficult to while realize that conversion shines up and down, thus the system that utilizes of the present invention can be applied to Antifalsification label material.
The invention also discloses one kind Lu containing lithium2Zr2O7System phosphor, the molecular formula of the phosphor For Yb/Eu/Er/Li: Lu2Zr2O7, the doping using the molar percent wherein doping of Yb as 10 ~ 30%, Eu is 1 ~ The doping of 10%, Er are 0.0001 ~ 0.01%, and the doping of the Li is 10 ~ 30%；The phosphor exists Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, excites in 365nm, 395nm and 420nm xenon lamp Under, obtain Eu3+Lower conversion red emission.
Preferably, the doping using the molar percent wherein doping of Yb as 15 ~ 25%, Eu is mixing for 3 ~ 8%, Er Miscellaneous amount is 0.0002 ~ 0.008%, and the doping of the Li is 15 ~ 25%.As further preferably, with molar percent wherein Yb Doping be 18 ~ 22%, Eu doping be 4 ~ 6%, Er doping be 0.0004 ~ 0.006%, the doping of the Li For 18 ~ 22%.
It is a kind of to prepare the Lu2Zr2O7The preparation method of system phosphor, this method comprise the following steps：
1）Will（10-25）% mMs of lutecium nitrate,（2-9）% mMs of ytterbium nitrate,（0.5-4）% mMs of europium nitrate,（0-0.5）% MM erbium nitrate, (5-10) % mMs of lithium acetate with（20-30）% mMs of citric acid is added to（4-10）Milliliter ethanol In, stirring obtains clear solution A in 30-60 minutes；
2）Will（40-50）% mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；
3）By 2）In solution exist（40-60）DEG C insulation（1-2）Hour, untill xerogel is obtained；
4）By 3）Middle gained xerogel grinding（30-60）After minute, it is positioned in Muffle furnace, and（700-900）DEG C sintering（4- 8）Hour, obtain final product after furnace cooling.
The phosphor is applied to optical anti-counterfeiting label material.
The present invention proposes to utilize Yb/Eu/Er/Li: Lu2Zr2O7System can be had under different-waveband shooting condition The feux rouges for having different spectrum shapes is realized false proof.The material can obtain shining for different colours under the shooting condition of different wave length. Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, excites in 365nm, 395nm and 420nm xenon lamp Under, obtain Eu3+Lower conversion red emission.The characteristics of system, has：A, system can be real under the excitation of the xenon lamp of different wave length Existing Eu3+Shine；B, system can realize that conversion shines up and down, and emission peak derives from different rare earth ions at the same time, have not Same glow color;C, due to Li+The introducing of ion substantially increases up-conversion fluorescence intensity, and nitre need not be added in raw material Sour erbium, utilizes the trace Er in ytterbium nitrate3+It can be achieved to shine, and usually a variety of rare earth ions be co-doped with matrix, due to dilute Larger radiationless cross-relaxation probability between native ion, it is difficult to while realize that efficient conversion up and down shines.Above feature Show that the system that the present invention utilizes can be applied to antifalsification label material.
The invention also discloses a kind of inorganic light-emitting device, using above-mentioned phosphor（The phosphor Can be that above-mentioned structural formula is Yb/Eu/Er/Li: Lu2Zr2O7And Yb/Eu/Er: Lu2Zr2One or both of O is mixed, Phosphor described below is the mixing of one or both of two kinds of structural formulas）Manufactured substrate.
The invention also discloses a kind of inorganic light-emitting device, including substrate and the inorganic luminescence thin film that is attached in substrate, The inorganic luminescence thin film is above-mentioned phosphor powders or phosphor thin slice.
The invention also discloses a kind of inorganic light-emitting device, including substrate and the inorganic luminescence thin film that is attached in substrate, The inorganic luminescence thin film is phosphor powders or phosphor thin slice.
Preferably, the thickness of inorganic luminescence thin film is 1-10mm.
The substrate of the present invention, can be rigid basement, or flexible substrates.Preferably, the rigid basement can PDMS (polydimethylsiloxanes can be selected from selected from glass, silicon, steel, ceramics, cement, timber and stone, the flexible substrates Alkane) film, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimides) film With PVA (polyvinyl alcohol) film.
Above-mentioned inorganic light-emitting device preparation method, including：By the outstanding of phosphor powders particle as described above Supernatant liquid is coated in substrate as described above.
Although suspension will be prepared into phosphor powders particle suspension liquid solvent as described above, it is then coated with In can prepare the light-emitting component that meets application claims in the substrate, but when also containing polymer in the suspension During matter, the sensitivity of final prepared light-emitting component and precision can be lifted further.
The content of the phosphor powders particle can also change in a wider scope, under preferable case, base In the suspension of 100 parts by weight, the content of the phosphor powders particle is 0.5-10 parts by weight, is preferably 1- 5 parts by weight.
Preferably, the polymer substance is selected from PVA, EVA (ethene-vinyl acetate copolymer), PDMS, PU, PMMA (gather Methyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), starch, cellulose, natural plant gum, animal One or more in glue, carboxymethyl starch, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose.
According to the present invention, the content of the polymer substance can also change in a wider scope, under preferable case, base In the suspension of 100 parts by weight, the high molecular content is 1-10 parts by weight, is preferably 3-8 parts by weight.
According to the present invention, the solvent can be various solvents commonly used in the art, be preferably selected from water, methanol, second Alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol phenyl ether, second two Alcohol benzyl oxide, health alcohol, diethylene glycol methyl ether, diethylene glycol ether, butyl carbitol, triethylene glycol methyl ether, diacetone alcohol, tridecanol, 14 Alcohol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, dimethylbenzene, bicyclohexyl, hexamethylene, n-butanol, One or more in butanone, repefral and D-sorbite.
According to the present invention, by the suspension of the phosphor powders particle coated in the side on the substrate surface Method can be the selection of this area routine, it is for instance possible to use the painting method such as spraying, spin coating, can also use printing technique. Present invention printing technique preferred herein prints the suspension of phosphor powders particle on the surface of the substrate, so that The sensitivity for the sensor being prepared and precision are further lifted.Wherein, the printing technique can be selected from dispensing, One kind in inkjet printing, water transfer, silk-screen printing and volume to volume printing.When using printing technique by the phosphor When the suspension of powder particle is printed on the surface of the substrate, the suspension is preferably prepared into ink, the preparation of the ink Method is by the way that the suspension blending and stirring or blending ultrasonic disperse are obtained.
The invention also discloses a kind of inorganic light-emitting device, which includes high molecular material and the nothing Machine luminescent material powder, phosphor powders are evenly distributed in high molecular material, the addition of phosphor powders Measure as 1 ~ 90%；Preferably 10 ~ 80%.High molecular material can be selected from PDMS (dimethyl silicone polymer), PET (poly- terephthaldehydes Sour glycol ester), PS (polystyrene), PU (polyurethane), PI (polyimides) and PVA (polyvinyl alcohol) it is thin.Appropriateness in order to Improve the performance of processing, which can also add coupling agent, lubricant, plasticizer etc..
The invention also discloses a kind of ink, which includes ink conventional ingredient and the phosphor powder End, phosphor powders are evenly distributed in ink conventional ingredient, and the addition of phosphor powders is 1 ~ 30%； Preferably 5 ~ 10%.Ink resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Either oiliness is oily Ink can also be water-based ink.
The invention also discloses a kind of coating, which includes coating conventional ingredient and the phosphor powder End, phosphor powders are evenly distributed in coating conventional ingredient, and the addition of phosphor powders is 1 ~ 30%； Preferably 5 ~ 10%.Coating resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Either oiliness applies Material can also be water paint.
In addition, it is formed at common paper, synthetic paper or epoxy resin, polyethylene by the way that phosphor will be included, gathers The macromolecule such as ethylene glycol terephthalate, polyester, polypropylene, polyvinyl chloride raw material, natural rubber or synthetic rubber, glass Glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete or combinations thereof and their fabricated product etc. Exterior trim surface, or by containing phosphor in inside.
Inorganic light-emitting device of the present invention can as illumination, for safety display utilization.For example,：Device vibrates The ligthing paraphernalias such as lamp, wind power lamp；Promptly, abnormal notification, very apparatus, very dangerous display, lamp, non-common mark, help work Mark, signboard, the display device of tool；Safety guard, the anxiety hung on around shop building are restricted, animal protective fence；Ladder Pedal, handrail and the mesh that is set in the state of road etc. is partly embedded in use filament；Health promoting appliance, walking assisting device Tool (walking auxiliary walking stick, the notification that shines antenna etc.)；The jewellery such as earrings, necklace；Support pillar, the railway Deng Jie roads machine of flag The exterior trim component for cutting road rod, bicycle, automobile, electric car, ship, aircraft etc. or build-in components, fishing tackle (simulation bait, fish Pole, fishing net etc.；Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy (float, buoy)；People, dog, The position display of the domestic animals such as the pets such as cat, ox, pig, sheep, chicken etc.；Fan (blade of wind-power electricity generation, ventilating fan etc. etc.), clothes (shoes, gym suit, manually shine cloth, artificial luminous filament, artificial luminescent fibre etc.)；Pack (case, stent, device, envelope, thickness Paper, crust packaging, exterior overlay film), (manually shine medical products (breathing assistance utensil, experimental study equipment) hair for robot Structure, artificial shiny skin, manually shine body) etc..As coating composition, ink composition, cement, surface dopant In the utilization example containing phosphor, can enumerate：In financial institution, community organization, credit card company, circulation industry etc. The mail piece such as crimping postcard sheet material containing phosphor in bonding agent use, stickup；The families such as chair, bed Tool；The building materials such as flooring material, ceramic tile, wall material, prefabricated board material, paveio(u)r, timber steel concrete；It is equipped on The automated navigation system device of vehicle；For operating the operation device of audio devices and air-conditioning etc.；Family's electrical article, Portable The input units such as device, electronic computer；Image storage means such as digital camera, CCD camera, film, photo, image etc..
By the appearance for making phosphor shine can produce new, therefore it is also contemplated for toy, lipuid goods etc. Entertain the expansion of commodity, daily necessities.For example,：Wind long narrow flag, swing, the fast ski-runnings such as dynamic toy, kite, carp shape flag Driving, carrousel, bow and arrow etc.；Pass through wind-force while the Powerless type light-emitting device (windbell etc.) of generation sound and light.Luminescent ball (golf, the ball of baseball, table tennis ball, the ball etc. of billiard ball), the windmill of luminous mechanism；Balloon；Laminated structure thing is paper , batch flute, paper folding, paper balloon, folding fan, New Year card, paint this；Sporting goods (jumping pole, fencing, the isometric size of bow and arrow Object etc.)；The score confirmation pressure sensitive sealant part of golf club, tennis court line tester, dynamic ornamentation body, dynamic are carved Carve, dynamic souvenir；Dynamic Display device；Luminous decorative device；The audio device such as loudspeaker, the musical instrument (string such as violin, guitar The diaphragms such as the wind instruments such as the percussion instruments such as musical instrument, xylophone, drum, trumpet, flute, glass), tuning fork etc.；Lipuid goods etc. entertain business Product；The water plant with sink etc., container are viewed and admired in aquarium；Luminous wrist watch, shine sand timer or sand timer type light-emitting device； Light emitting-type simulates candle device；The artificial plant that can be shone；Artificial eye；Cosmetic composition containing adhesion polymer, The printed article and marketable securities, the printer's ink containing inorganic light-emitting particle, bill, branch of forgery can be distinguished under visual state Ticket, stock, bond, various security, exchange ticket, books certificate, the ticket of traffic organization, toll facility, the admission ticket of project, coloured silk Middle lottery ticket of ballot certificate that ticket, Public Physical Education are competed etc., bank note, identity card, ticket, the pass etc., passport, the organic ciphertext book of writing Printed article or seal seal etc..
Using shining with phosphor, make to be attached to phosphor surface photochemical catalyst activation and Obtain, phosphor body-photochemical catalyst complex can be used for：Antibacterial, sterilization, treatment to non-human animal, vehicle are helped The dirt purification of the antibacterial articles such as hand strap, handle, the energy of flow using the fluid of wall inside pipe arrangement positioned at dark place etc. The purification of amount.Inorganic luminous substance activates the photocrosslinking agent in macromolecule resin, can also promote to be crosslinked by shining.
By the way that with being mixed in resin, the phosphor of the present invention can be formed the resin combination of the present invention.
In addition, formed again by further adding other inorganic material or organic material in the resin combination of the present invention Condensation material, can also form the phosphor body of the present invention.
For example, in the case that resin is epoxy resin, acrylic resin etc., relative in the compounding of 100 mass parts of resin 1~200 part of phosphor is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to resin 100 mass parts are compounded above-mentioned 30~300 mass parts of phosphor.Blend can be mixed by using conical mixer, V-type The mixers such as conjunction machine, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill make resin combination.
In addition, in the case of forming phosphor body by the resin combination, such as when obtaining the phosphor body of sheet, Such as relative to 100 parts by weight of Corvic, it is compounded above-mentioned 50~200 mass parts of phosphor, calcium-zinc system and stablizes 3~5 mass parts of agent, 30~100 mass parts of dioctyl phthalate as plasticizer, with two-roller mill at 150~200 DEG C It is kneaded, so as to obtain the phosphor body with flexible sheet.
When obtaining the phosphor body of film-form, such as relative to 100 mass parts of pet resin, Above-mentioned 20~50 mass parts of phosphor are compounded, are carried out with double screw extruder, inflation processing machine at 250~300 DEG C It is kneaded, shaping, so as to obtain the phosphor body of film-form.
When obtaining the phosphor body of other shapes, such as relative to 100 mass parts of acrylic resin, it is compounded inorganic light-emitting 5~100 mass parts of material, are kneaded at 170~200 DEG C with double screw extruder, are molded, so as to obtain banding, Tabular, bar-shaped, partical phosphor body.In addition, by using injection (mo(u)lding) machine at 170~200 DEG C to partical Phosphor body is processed shaping, can obtain the phosphor body of three-dimensional shape.
As above-mentioned resin or other organic materials, can enumerate：Resin as thermoplastic resin, thermosetting resin. As thermoplastic resin, for example,：Low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear, low density The polyethylene such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene- The polyamide such as the styrene polymers such as styrol copolymer (ABS resin) or copolymer, 6- nylon, 66- nylon, 12- nylon, gather The acrylic resins such as amide imide, polyimides, polyetherimide, polyurethane, polymethyl methacrylate, poly- acetic acid second The fluororesin such as enester, vinyl-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), alkenyl aroma hydroxy-aromatic resin, gather The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polylactic acid, bisphenol-A Be the makrolon such as makrolon, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, It is the polyacrylic acid such as polyacrylonitrile, styrene-acrylonitrile copolymer (AS resins), polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, poly- Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, copolymer, ethene or the propylene of liquid crystal polymer ethene and propylene With copolymer, ethene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene etc.) With the copolymer of monomer (vinyl acetate, acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl alcohol etc.) Deng.
Thermoplastic resin can be used alone or in combination of two or more kinds.It should be noted that thermoplastic resin is copolymerization Can be the copolymer of any forms such as random copolymer, block copolymer during thing.As thermosetting resin, can enumerate：Phenol Urea formaldehyde, urea resin, melmac, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, Organic siliconresin, alkyd resin, polyimides, polyaminobismaleimide, casein resin, furane resins, polyurethane resin Deng.It can additionally enumerate：Utilize ultraviolet, the resin of radiation curing.
And then it can enumerate：Natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
In addition, can be by pigment, dyestuff, lubricant, antioxidant, ultra-violet absorber, light stabilizer, antistatic Agent, fire retardant, fungicide, antiseptic, curing catalyst, Photoepolymerizationinitiater initiater etc. are together with the phosphor of the present invention Mixing, is shaped to bar-shaped, tabular, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, flakey, piece The arbitrary shapes such as shape, liquid, gelatinous, sol form, suspension, aggregation, capsule-type.
As pigment, inorganic pigment, organic pigment can be enumerated.
As inorganic pigment, can enumerate：Titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Kermes (red iron oxide (III)), cadmium red, ultramarine, dark blue, chrome oxide green, cobalt green, chocolate, titanium is black, synthesis is iron black, carbon black, Mica, the aluminium oxide covered by titanium oxide, iron oxide, mica, glass flake, the holographic pigment covered by titanium oxide, iron oxide Deng.In addition, as metallic powdery pigment, can enumerate：Aluminium powder, copper powders, powder of stainless steel, metallic colloid, conduct There are transparent emerylite, coloring mica, interference mica, interference aluminium oxide, the interference silica (interference glass) of interference effect Deng.
As organic pigment, can enumerate：Azo pigment (monoazo yellow, condensation azophosphine, azomethine Huang etc.), Huang Color iron oxide, titan yellow, pucherite, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Huang etc. Yellow uitramarine；The orange pigments such as permanent orange；Red iron oxide, naphthols AS systems azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purple face such as cobalt violet, quinacridone violet, dioxazine violets Material；The blue pigments such as cobalt blue, phthualocyanine pigment (phthalocyanine blue etc.), anthracene indigo plant；The viridine greens such as phthalocyanine green, azo system disperse dyes, Organic dyestuff such as anthraquinone system disperse dyes etc..
As dyestuff, can enumerate：Azo dyes, anthraquinone dye, bipseudoindoxyl dye, sulfur dye, triphenhlmethane dye, Pyrazolone dye, Stilbene dyestuff, diphenylmethane dye, Xanthene dyes, alizarin dyes, acridine dye, quinoneimine dye (piperazine Dyestuff, oxazine dyes, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
As antioxidant, can enumerate：Hindered phenol series compound, phosphite ester based compound, phosphinate system chemical combination Thing and thioether based compound etc..
As hindered phenol series compound, can enumerate：Alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic ester, the 2- tert-butyl groups -6- (3 '-tert-butyl group -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyls acrylate, 2,6- di-t-butyls -4- (N, N- dimethylaminomethyl) phenol, bis- uncles of 3,5- Butyl -4- benzylphosphonic acids diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl phenols), 4,4 '-methylene-bis(2,6-di-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylene-bis- (6- Alpha-Methyls-benzyl-paracresol) 2,2 '-ethidine-bis- (4,6- di-t-butyls Phenol), 2,2 '-butane-bis- (4- methyl-6-tert-butylphenols), 4,4 '-butane double (3 methy 6 tert butyl phenol), Double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters of triethylene glycol-N-, double [3- (the bis- tertiary fourths of 3,5- of 1,6-HD Base -4- hydroxy phenyls) propionic ester], double [the 2- tert-butyl group -4- methyl 6- (the 3- tert-butyl group -5- methyl -2- hydroxybenzyls) phenyl] it is right Double { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono the epoxide] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (the 6- tert-butyl groups-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), double (3,5- di-t-butyl -4- hydroxyl benzyls Base) thioether, 4,4 '-two thio bis(2,6-di-butyl phenol)s, 4,4 '-three thio bis(2,6-di-butyl phenol)s, 2,2- Double (just pungent sulfenyl) -6- (the 4- hydroxyls of thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,4- Base -3 ', 5 '-di-tert-butyl amido) -1,3,5- triazines, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy groups Cinnamamide), N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionos] hydrazine, (2- methyl -4- the hydroxyls of 1,1,3- tri- Base -5- tert-butyl-phenyls) butane, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid esters, 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono epoxide] ethyl isocyanurate and four [methylene -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic esters] Methane etc..
As phosphite ester based compound, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid can be enumerated Three decyl esters, phosphorous acid trioctylphosphine ester, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid two are pungent Base mono-phemyol ester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, Phosphorous acid list octyl diphenyl, phosphorous acid three (diethyl phenyl) ester, phosphorous acid three (diisopropyl phenyl) ester, phosphorous acid three (di-n-butyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid three (2,6- di-tert-butyl-phenyls) ester, two Stearyl pentaerythritol diphosphites, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (bis- tertiary fourths of 2,6- Base -4- aminomethyl phenyls) pentaerythritol diphosphites, double (2,6- di-t-butyl -4- ethylphenyls) pentaerythrite diphosphorous acids Ester, double { double (1- methyl isophthalic acids-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, double (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..It is used as other Phosphite ester based compound, can enumerate and be reacted with dihydric phenol class so as to the phosphite ester based compound with cyclic structure.
As phosphinate based compound, can enumerate：Four (2,4- di-tert-butyl-phenyls) -4,4 '-biphenylene two is sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyls) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylen, four (2,6- di-tert-butyl-phenyls) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylen, the sub- phosphine of four (2,6- di-tert-butyl-phenyls) -3,3 '-biphenylene two Acid esters, double (2,4- di-tert-butyl-phenyls) -4- phenyl-phenyls phosphinates, double (2,4- di-tert-butyl-phenyls) -3- phenyl-benzene Base phosphinate, double (2,6- di-n-butyls phenyl) -3- phenyl-phenyls phosphinates, double (2,6- di-tert-butyl-phenyls) -4- benzene Base-phenylphosphite ester and double (2,6- di-tert-butyl-phenyls) -3- phenyl-phenyl phosphinates etc..
As thioether based compound, can enumerate：Thiodipropionate dilauryl, thio-2 acid two (tridecyl) Ester, thio-2 acid myristyl ester, thio-2 acid distearyl base ester, (the 3- lauryl propane thioic acids of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionates), pentaerythrite-four (3- octadecyls thiopropionate), season penta Tetrol four (3- myristyls thiopropionate) and pentaerythrite-four (3- stearyl-thios propionic ester) etc..As comprising ultraviolet The light stabilizer of light absorbers, can enumerate：Benzophenone based compound, benzotriazole based compound, aromatic series benzoic ether Based compound, oxanilide based compound, cyanoacrylate based compound and the amine compound that is obstructed etc..
As benzophenone based compound, can enumerate：Benzophenone, 2,4 dihydroxyl benzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyls benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl group -5- sulphurs Acyl group benzophenone, 5- chlorine-2-hydroxyls benzophenone, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl groups -2 ' - Carboxyl benzophenone and 2- hydroxyls -4- (2- hydroxy-3-methyls-acryloxy isopropoxy) benzophenone etc..
As benzotriazole based compound, can enumerate：2- (5- methyl -2- hydroxy phenyls) benzotriazole, 2- (3,5- bis- The tert-butyl group -2- hydroxy phenyls) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyls of 3,5-) benzotriazole, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyls of 3,5-) -5- chlorobenzotriazoles, 2- (the 5- tert-butyl group -2- hydroxy phenyls) benzotriazole, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] -2H- benzotriazole and 2- (4 '-octyloxies -2 '-hydroxyl Phenyl) benzotriazole etc..
As aromatic series benzoic ether based compound, can enumerate：Salicylic acid is to tert-butyl benzene base ester, salicylic acid to octyl group Salicylic acid alkyl phenyl esters such as phenylester etc..
As oxanilide based compound, can enumerate：2- ethyoxyls -2 '-ethyloxanilide, 2- ethyoxyls -5- The tert-butyl group -2 '-ethyloxanilide and 2- ethyoxyls -3 '-dodecyl butoxanilide etc..
As cyanoacrylate based compound, can enumerate：Ethyl -2- cyano group -3,3 '-diphenylacrylate ester, 2- Ethylhexyl-cyano group -3,3 '-diphenylacrylate ester etc..
As the amine compound that is obstructed, can enumerate：4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl ketos Base -2,2,6,6- tetramethyl piperidines, 4- acryloxy -2,2,6,6- tetramethyl piperidines, 4- (phenylacetyl epoxide) -2,2,6, 6- tetramethyl piperidines, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidines, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl epoxide -2,2,6,6- tetramethyl piperidines, 4- benzyls epoxide -2,2, 6,6- tetramethyl piperidines, 4- phenoxy group -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl epoxide) -2,2,6,6- tetramethyls Phenylpiperidines, 4- (cyclohexyl carboxyamide epoxide) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl epoxide) -2,2,6, 6- tetramethyl piperidines, double (2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, double (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, double (2,2,6,6- tetramethyl -4- piperidyls) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Double (2,2,6,6- tetramethyl -4- piperidyls) adipate esters, double (2,2,6,6- tetramethyl -4- piperidyls) terephthalates, 1,2- double (2,2,6,6- tetramethyl -4- piperidyls epoxide)-ethane, α, α '-bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen Base)-paraxylene, double (2,2,6,6- tetramethyl -4- piperidyls)-toluylene -2,4- diurethanes, it is double (2,2, 6,6- tetramethyl -4- piperidyls)-hexa-methylene -1,6- diurethanes, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic esters, three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono epoxide } -2,2,6,6- tetramethyl piperidines and 1,2,3,4- butane tetracarboxylic acid and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidines and β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiros (5,5) of 2,4,8,10- 11 Alkane] dimethanol condensation product etc..
As antistatic additive, can enumerate：The toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are answered Close the metal oxygens such as oxide, indium tin composite oxides, the electric conductivity indium oxide for being doped with Sn, F, Cl etc., tin oxide, zinc oxide Inorganic system's antistatic additive such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-bay Acid amides propiono) quaternary ammonium salt system, sulfonate based compound, the alkyl phosphate such as trimethyl ammonium sulfate, neopelex Antistatic additive of the organic systems such as based compound etc..
As fire retardant, can enumerate：Bromide fire retardant, phosphorus flame retardant, chlorine-based flame retardant, triazine flame retardant, with And other inorganic flame retardants such as salt of phosphoric acid and piperazine etc..
As bromide fire retardant, can enumerate：Brominated Polystyrene, brominated polyacrylate, brominated polyphenylether, bromination are double Phenol A types epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, be used as the polycarbonate oligomer of Material synthesis, two phthalimide chemical combination of bromination using brominated bisphenol A The compounds such as the brominated diphenyl base alkane such as thing, bromination Biphenyl Ether and 1,2- bis- (penta-bromophenyl) ethane.Wherein it is possible to enumerate：Poly- three The brominated Polystyrenes such as bromstyrol, poly- (dibromobenzene aether), decabrominated dipheny base ether, double (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethene-bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
As phosphorus flame retardant, can enumerate：Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2- second Base hexyl) ester, tributoxyethyl phosphate, triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, phosphoric acid Three (isopropyl phenyl) esters, tricresyl phosphate (phenyl) ester, tricresyl phosphate naphthyl ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyls) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyls phosphate ester acid, 2- methacryloxyethyls phosphate ester acid, diphenyl -2- acryloyls Epoxide ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyls phosphate, melamine phosphate, two (melamines) Phosphate, melamine pyrophosphoric ester, triphenylphosphine oxide, trimethylphenyl phosphine oxide, methanephosphonic acid diphenyl ester, phenyl-phosphonic acid two The phosphates such as ethyl ester, resorcinol Polyphenyl phosphate, 1,3- phenylenes double (2,6- dimethylphenylphosphates), resorcinols Poly- (two -2,6- xylyls) phosphate, polymer with bis phenol A tolyl phosphate, bisphenol-A Polyphenyl phosphate, the poly- (2,6- bis- of quinhydrones Tolyl) condensed phosphoric acid esters such as the aromatic condensation phosphate such as phosphate and their condensation product etc..
As chlorine-based flame retardant, can enumerate：Five cyclodecane of pentachloro-, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..As triazine flame retardant, can enumerate：Melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- Diaminourea -6- nonyl -1,3,5- triazines, 2,4- diaminourea -6- hydroxyl -1,3,5- triazines, 2- amino -4,6- dihydroxy -1,3, 5- triazines, 2,4- diaminourea -6- methoxyl group -1,3,5- triazines, 2,4- diaminourea -6- ethyoxyl -1,3,5- triazines, 2,4- diaminos Base -6- propoxyl group -1,3,5- triazines, 2,4- diaminourea -6- isopropoxy -1,3,5- triazines, 2,4- diaminourea -6- sulfydryl -1, 3,5- triazines and 2- amino -4,6- dimercapto -1,3,5- triazines etc..
As phosphoric acid and the salt of piperazine, can enumerate：Orthophosphoric acid piperazine, piperazine pyrophosphate and polyphosphoric acid piperazine etc..
As inorganic flame retardant, can enumerate：The antimonials such as antimony trioxide, Antimony pentachloride, zinc borate, Boratex, Aluminium hydroxide, magnesium hydroxide and red phosphorus etc..
As fungicide, can enumerate：The copper fungicides such as copper 8-hydroxyquinolinate, zineb (Zineb), maneb (Maneb) etc. have The organochlorine such as machine thiophanate fungicide, captan, Bravo system fungicide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximide system such as benzimidazole system fungicide, iprodione, vinclozolin, procymidone fungicide, furametpyr The morpholine system fungicide such as the phenylpyrrole such as amine system fungicide, fludioxonil system fungicide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidine system fungicide such as the methoxy acrylate such as ORIBRIGHT system fungicide, mepanipyrim, cyprodinil, pyrimethanil, The soil fungicides such as the ergosterol biosynthesis inhibitors such as triazolone, fluorine bacterium azoles, trichloronitromethane, PCNB and fluorine pyridine Amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2- double (acetyl bromide epoxide) ethane, cinnamic acid, acetic acid benzene The bromo- 3- itrile groups propionyl of ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
As antiseptic, can enumerate：Make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Inorganic system's powder obtained from compound.As load, can enumerate：Zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..It can in addition contain enumerate：With phosphate, boric acid system, silicic acid system Be respectively glass one kind or two or more glass as glass forming constituents in containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate：Aliphatic acid, fatty acid metal salts, oxo aliphatic acid, paraffin, low molecular weight it is poly- Alkene, fatty acid amide, alkylenebisfatty acid amides, aliphatic ketone, fatty acid part saponification ester, aliphatic acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethanol ester and modified organic silicon etc..
As aliphatic acid, can enumerate：Oleic acid, stearic acid, laurate, hydroxy stearic acid, behenic acids, arachidonic acid, The aliphatic acid of the carbon numbers 6~40 such as linoleic acid, leukotrienes, ricinoleic acid, palmitic acid, montanic acid and their mixture.As fat Fat acid metal salt, can enumerate：It is sodium laurate, potassium laurate, Magnesium dilaurate, calcium laurate, zinc laurate, barium laurate, hard Resin acid sodium, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, behenic acid sodium, behenic acid potassium, behenic acids Alkali (soil) gold of the aliphatic acid of carbon number 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acids barium, montanic acid sodium and montanic acid calcium Belong to salt.
As oxo aliphatic acid, can enumerate：1,2- stearoxylic acids etc..
As paraffin, can enumerate：The paraffin of the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline more than 18.
As the polyolefin of low molecular weight, can enumerate：Tissuemat E, maleic acid modified Tissuemat E, the poly- second of oxidized form The polyolefin of alkene wax, haloflex wax and polypropylene wax equimolecular quantity below 5000., specifically can be with as fatty acid amide Enumerate：The fatty acid amide of the carbon numbers more than 6 such as oleamide, erucic amide, Shan Yu acid amides.
As alkylenebisfatty acid amides, can enumerate：Methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty acid amides of the carbon numbers more than 6 such as double (2- hydroxyethyls) stearmides.
As aliphatic ketone, can enumerate：The aliphatic ketone of the carbon numbers such as higher aliphatic ketone more than 6.As fatty acid moieties Divide saponification ester, can enumerate：Partly-hydrolysed ester of montanic acid etc..
As aliphatic acid low-carbon-ester, can enumerate：Stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acids ester, arachidonate, montanate and isostearate etc..
As polyol esters of fatty acids, can enumerate：Glycerine tristearate, glycerine distearate, glycerine Monostearate, pentaerythritol tetrastearate, pentaerythrite tristearate, two myristinate of pentaerythrite, Ji Wusi Alcohol monostearate, pentaerythritol adipate stearate and anhydrous sorbitol Dan behenic acid esters etc..
As fatty acid polyglycol ethanol ester, can enumerate：Cithrol, polytrimethylene diol fatty acid ester and Polypropylene glycol fatty acid esters etc..
As modified organic silicon, can enumerate：The alkoxy-modified organosilicon of organic silicon modified by polyether, higher fatty acids, contain Organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness for having higher fatty acids have Machine silicon etc..
As curing catalyst, can enumerate：(peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and organic peroxide, octyl group acid tin, the dibutyl such as azo-compound (azodiisobutyronitrile and azobisisovaleronitrile etc.) Tin two (2 ethyl hexanoic acid ester), dioctyl tin two (2 ethyl hexanoic acid ester), dioctyl tin diacetate esters, dibutyltindilaurylmercaptide cinnamic acid Ester, dioctyl tin dilaurate, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid Lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, 2 ethyl hexanoic acid lead lead octoate and four The inorganic acids such as Organometallic derivatives, hydrochloric acid, nitric acid, the sulfuric acid such as the metals such as n-butyl titanate and organic and inorganic acid salt, The sulfoacid compounds such as p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, sulfoacid compound Amine corrective, organic amine, phosphoric acid, the pyrophosphoric acid such as triethylamine etc., phosphate monoester or di-phosphate ester etc..As phosphate monoester, For example,：Mono-octyl phosphate, mono phosphoric acid ester propyl ester and mono phosphoric acid ester lauryl etc..As di-phosphate ester, for example,： Dioctylphosphoric acid ester, phosphoric acid dipropyl and didodecyl phosphate etc..And then it can enumerate：Single (2- (methyl) acryloxy second Base) phosphate cpd, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
As Photoepolymerizationinitiater initiater, can enumerate：(2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propanes - 1- ketone, 1- hydroxycyclohexylphenylketones, benzoin alkylether etc.), benzoyl formic acid ester compounds (methylbenzoyl formate Deng), thioxanthone compounds (isopropyl thioxanthone etc.), benzophenone cpd (benzophenone etc.), phosphate compound (1,3, 5- trimethylbenzoyl diphenyl phosphine oxides etc.) and benzil dimethyl ketal etc..
And then coating is mixed in so as to the inorganic hair that the present invention can also be made by the way that the phosphor of the present invention is matched somebody with somebody Photosensitiveness coating composition.
The inorganic light-emitting coating composition of the present invention can be coated with the surface of other materials.
In addition, the luminosity of the inorganic light-emitting coating composition of the invention of the phosphor containing the present invention Height, therefore visual high application can be carried out.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root It can also contain according to needs：Solvent, dispersant, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoamer, The coating such as antioxidant, the light stabilizer comprising ultra-violet absorber, fire retardant, curing catalyst, fungicide and antiseptic Use additive.
As the material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet can also be used The various resins such as curable resin, radiation curing resin, for example,：Acrylic resin, alkyd resin, poly- ammonia Ester resin, polyester resin, amino resins etc., organosilicon acid esters, organic titanate etc..
As black film formation material, can enumerate：Polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
As solvent, can enumerate：Aliphatic hydrocarbon, aromatic hydrocarbon (C7~10, such as toluene, dimethylbenzene and ethyl Benzene), ester or ether-ether (C4~10, such as methoxybutyl acetic acid esters), ether (C4~10, such as tetrahydrofuran, single ethyl of EG Ether, the single-butyl ether of EG, single ethylether of the monomethyl ether of PG and DEG), (C3~10, such as methyl iso-butyl ketone (MIBK), two are just for ketone Butyl ketone), alcohol (C1~10, such as methanol, ethanol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohols), acid amides (C3~6, such as dimethylformamide, dimethylacetylamide, 1-methyl-2-pyrrolidinone), sulfoxide (C2~4, such as dimethyl sulfoxide (DMSO)) and their mixed solvent of more than two kinds, water or foregoing mixed solvent.As scattered Agent, as long as being macromolecule dispersing agent, can enumerate：The formal of naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] Woods condensation product, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2~4) carboxylic acid (Malaysia Acid/glycerine/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~10000) and polyethylene Alcohol (Mn2000~100000) etc..
As low molecule dispersant, following substances can be enumerated.
(1) poly (oxyalkylene) fundamental mode
Aliphatic alcohol (C4~30), [alkyl (C1~30)] phenol, aliphatic (C4~30) amine and aliphatic (C4~30) acid amides 1~30 mole of addition product of AO (C2~4).
As aliphatic alcohol, there are n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, octanol, dodecanol etc.；As (alkane Base) phenol, there are phenol, methylphenol and nonyl phenol etc.；As aliphatic amine, there are lauryl amine and methyl stearic amine etc.； With as aliphatic amide, there is stearmide etc..
(2) polyol type
The aliphatic acid (laurate, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, D-sorbite And anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the aliphatic acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulfuric ester of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol Alkali metal (same as described above) salt etc..
(5) sulfonate type
Sulfonate alkali metal (same as described above) salt of [alkyl (C1~30)] phenol (same as described above).
(6) phosphate type
The monophosphate of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol The salt of ester or bisphosphate [alkali metal (same as described above) salt, quaternary ammonium salt etc.].
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and the tertiary amine (dimethylstearamine of C4~30 Deng)] inorganic acid (hydrochloric acid, sulfuric acid, the nitric acid of the monoesters of hydrochloride, triethanolamine and the aliphatic acid of C4~30 (same as described above) With phosphoric acid etc.) salt.
(8) quaternary
The inorganic acid of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 (same as described above) salt etc..
As inorganic dispersant, can enumerate：Alkali metal (same as described above) salt and phosphate dispersant (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
As filler, can enumerate：It is inorganic as the oxide system of representative using silica, aluminium oxide, zirconium oxide, mica The organic compounds such as the micro mist or acrylic resin, fluororesin of the non-oxidized substance based inorganic material such as thing, carborundum, silicon nitride.Separately Outside, the metal dusts such as aluminium, zinc, copper can also be added according to purposes.And then as the concrete example of filler, it can enumerate：Dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based material；Synthesize amorphous silica；Kaolinite, mica, talcum, wollastonite, asbestos, calcium silicates, silicic acid The silicates such as aluminium；The vitreums such as glass powder, glass marble, hollow glass ball, glass flake, bulb glass ball；Boron nitride, carbonization The non-oxidized substance based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, carborundum, titanium boride, titanium nitride, titanium carbide；Calcium carbonate； The metal oxides such as zinc oxide, aluminium oxide, magnesia, titanium oxide, beryllium oxide：Barium sulfate, molybdenum disulfide, tungsten disulfide, fluorination The inorganic matters such as carbon；The metal dusts such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Deng carbon body etc..
As thickener, can enumerate：Montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic filler such as aluminium system thickener, methylcellulose, carboxymethyl cellulose, hexyl methyl cellulose, hydroxyethyl cellulose, hydroxyl The cellulose-based thickeners such as propyl cellulose, polyurethane resin system thickener, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene The polyethers trees such as the polyethylene-based thickener such as benzyl ether copolymer, polyethers dialkyl ester, polyethers dialkyl ether, the epoxide modified thing of polyethers The association thickeners such as fat system thickener, urethane-modified polyether system, polyurethane resin system of polyether polyol system etc. are special The eggs such as the surfactant such as macromolecule nonionic thickener, nonionic system system thickener, casein, casein acid sodium, casein acid ammonium Acrylic thickeners such as white matter system thickener and mosanom etc..
As levelling agent, can enumerate：PEG types nonionic surfactant (nonyl phenol EO1~40 mole addition product, Stearic acid EO1~40 mole addition product etc.), polyol-based non-ionic surfactant (anhydrous sorbitol palm acid monoester, dehydration Sorbierite stearate monoesters, three ester of anhydrous sorbitol stearic acid etc.), fluorine-containing surfactant (perfluoroalkyl EO1~50 mole plus Into thing, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
For curing agent, as the curing agent of polyalcohols, can enumerate：Hexamethylene diisocyanate, trimethyl six Methylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, two isocyanide of diphenyl methane Acid esters, xylylene diisocyanate, hydrogenation xylylene diisocyanate, toluylene diisocya-nate, hydrogenation first generation Phenylene vulcabond, lysine diisocyanate, the nurate bodies of polyisocyanate compound, buret bodies, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propane diols, trimethylolpropane, by blocked polyisocyanic acid The monomers such as ester curing agent or mixture of more than two kinds, their polyalcohol addition product, their copolymer, block polymer etc. Like that at normal temperatures being capable of cured isocyanates.As the curing agent of epoxy resin, can enumerate：Acid anhydrides, phenolic aldehyde tree Fat, polyamide, amine additives, urea resin, melmac and isocyanates etc..
As crosslinking agent, can enumerate：The more isocyanides of melmac, urea resin, polyisocyanate compound, block Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Fat and hexamethoxy methylated melamine, N, N, N ', N '-tetrakis hydroxymethyl phosphonium succinamide, tetramethoxymethylization urine Element, 2,4,6- tetrakis hydroxymethyl phosphonium phenol etc. have the compound of hydroxymethyl and methoxy or ethoxyl methyl etc..
As pigment, in addition to aforesaid pigments, can also enumerate：Vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Deng vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid thing, one hydrogen magnesium of phosphoric acid, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid thing, phosphorus Sour magnesium cobalt eutectoid thing, magnesium phosphate nickel eutectoid thing, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid thing, three polyphosphoric acid aluminum dihydrogens, three The phosphate metals such as polyphosphoric acid magnesium, the magnesia processed material of three polyphosphoric acid aluminum dihydrogens, the magnesia processed material of three polyphosphoric acid dihydro zinc The silica modified chemical combination of magnesium phosphate as the processed material of the magnesium-containing compound of salt and then silica modified magnesium phosphate etc. The phosphate-based rust resisting pigment such as thing；The rust resisting pigment containing zinc component such as trbasic zinc phosphate, magnesium handle three polyphosphoric acid aluminum dihydrogens, Calcium treatment Calcium phosphate etc. is without zinc rust resisting pigment；The calcium silicates such as the composite calcium silicate comprising calcium orthosilicate component or calcium metasilicate component；Calcium from Son exchanges silica, magnesium ion exchanges the metal ion exchanged silica such as silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoamer, for example,：Silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness gather The silicon-type such as siloxanes defoamer, mineral oil system defoamer, non-organic silicon polymer system defoamer, comprising changing selected from organic At least one kind of defoamer in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol for including carbon number more than 18 Defoamer etc..
Light stabilizer, fire retardant, curing catalyst, fungicide for antioxidant, comprising ultra-violet absorber and Antiseptic etc., can enumerate aforementioned substances.
Brief description of the drawings
Yb/Er/Eu in Fig. 1, embodiment 1:The X-ray diffractogram of Lu2Zr2O7.
Yb/Er/Eu in Fig. 2, embodiment 1:Room temperature PL spectrum figures of the Lu2Zr2O7 under the excitation of 980 nanometer lasers.
Yb/Er/Eu in Fig. 3, embodiment 1:Room temperature PL spectrum figures of the Lu2Zr2O7 in the case where 365 nanometers of xenon lamps excite.
Yb/Er/Eu in Fig. 4, embodiment 1:Room temperature PL spectrum figures of the Lu2Zr2O7 in the case where 395 nanometers of xenon lamps excite.
Yb/Er/Eu in Fig. 5, embodiment 1:Room temperature PL spectrum figures of the Lu2Zr2O7 in the case where 420 nanometers of xenon lamps excite.
Yb/Er/Eu/Li in Fig. 6, embodiment 6:The X-ray diffractogram of Lu2Zr2O7.
Yb/Er/Eu/Li in Fig. 7, embodiment 6:Room temperature PL spectrums of the Lu2Zr2O7 under the excitation of 980 nanometer lasers Figure.
Yb/Er/Eu/Li in Fig. 8, embodiment 6:Room temperature PL spectrums of the Lu2Zr2O7 in the case where 365 nanometers of xenon lamps excite Figure.
Yb/Er/Eu/Li in Fig. 9, embodiment 6:Room temperature PL spectrums of the Lu2Zr2O7 in the case where 395 nanometers of xenon lamps excite Figure.
Yb/Er/Eu/Li in Figure 10, embodiment 6:Room temperature PL spectrums of the Lu2Zr2O7 in the case where 420 nanometers of xenon lamps excite Figure.
Embodiment
Embodiment 1
By 1.52 mMs of lutecium nitrates, 0.3 mM of ytterbium nitrate, 0.18 mM of europium nitrate, 0.002 mM of erbium nitrate and 2 mMs of citric acids are added in 8 milliliters of ethanol, are stirred 30 minutes；Then 30 points of 2 mMs of basic zirconium chlorides and stirring are added Clock；50oXerogel is obtained when insulation 2 is small at a temperature of C；Xerogel is ground 30 minutes, is then placed in Muffle furnace, in 700oWhen C insulations 4 are small, final product is obtained after furnace cooling.
Powder x-ray diffraction analysis show：Products therefrom is pure Emission in Cubic Lu2Zr2O7（Fig. 1）.Irradiated in 980nm laser Under, Yb/Er/Eu: Lu2Zr2O7It can obtain Er3+Ion becomes clear yellow emission, and faint Eu is included in spectrum3+Shine ripple Section（Fig. 2）.In 365nm（Fig. 3）、395nm（Fig. 4）With 420nm（Fig. 5）Under xenon lamp shooting condition, Eu can be obtained3+Bright Red emission.
Embodiment 2
By 1.68 mMs of lutecium nitrates, 0.2 mM of ytterbium nitrate, 0.12 mM of europium nitrate, 0.005 mM of erbium nitrate with And 2 mMs of citric acids are added in 8 milliliters of ethanol, stir 30 minutes；Then 30 points of 2 mMs of basic zirconium chlorides and stirring are added Clock；Xerogel is obtained when insulation 2 is small at a temperature of 50 DEG C；Xerogel is ground 30 minutes, is then placed in Muffle furnace, in When 700 DEG C of insulations 4 are small, final product is obtained after furnace cooling.
Embodiment 3
By 1.42 mMs of lutecium nitrates, 0.5 mM of ytterbium nitrate, 0.08 mM of europium nitrate, 0.001 mM of erbium nitrate with And 2 mMs of citric acids are added in 8 milliliters of ethanol, stir 30 minutes；Then 30 points of 2 mMs of basic zirconium chlorides and stirring are added Clock；Xerogel is obtained when insulation 2 is small at a temperature of 50 DEG C；Xerogel is ground 30 minutes, is then placed in Muffle furnace, in When 700 DEG C of insulations 4 are small, final product is obtained after furnace cooling.
Embodiment 4
50 grams of the luminescent material of embodiment 1 is weighed, with 150 grams of ink vehicles (phenolic resin oil 80 grams, alkyd resin oil 40 Gram, 30 grams of light resinon), appropriate amount of addition agent (8 grams of varnish, 0.5 gram of naphthoic acid cobalt) be mixed, rolled on three roller ink grinding mills System, prepares offset ink.Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, in 365nm, 395nm is with the excitation of 420nm xenon lamps, obtaining Eu3+Lower conversion red emission.
Embodiment 5
18% powder of stainless steel is added in the luminous anti-forgery ink of embodiment 4, according to known ink processing method, can be made into print Brush ink, except Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, in 365nm, 395nm with Under the excitation of 420nm xenon lamps, Eu is obtained3+Lower conversion red emission.Also there is the antiforge function of magnetic characteristic.
Embodiment 6
By 1.52 mMs of lutecium nitrates, 0.3 mM of ytterbium nitrate, 0.18 mM of europium nitrate, 0.002 mM of erbium nitrate, 0.2 mM of lithium acetate and 2 mMs of citric acids are added in 8 milliliters of ethanol, are stirred 30 minutes；Then 2 mMs are added Basic zirconium chloride simultaneously stirs 30 minutes；50oXerogel is obtained when insulation 2 is small at a temperature of C；By xerogel grind 30 minutes, so After be placed in Muffle furnace, in 700oWhen C insulations 4 are small, final product is obtained after furnace cooling.
Powder x-ray diffraction analysis show：Products therefrom is pure Emission in Cubic Lu2Zr2O7（Fig. 6）.Irradiated in 980nm laser Under, Yb/Er/Eu/Li: Lu2Zr2O7It can obtain Er3+Ion becomes clear yellow emission, and faint Eu is included in spectrum3+Shine Wave band（Fig. 7）.In 365nm（Fig. 8）、395nm（Fig. 9）With 420nm（Figure 10）Under xenon lamp shooting condition, Eu can be obtained3+It is bright Bright red emission.
Embodiment 7
By 1.68 mMs of lutecium nitrates, 0.2 mM of ytterbium nitrate, 0.12 mM of europium nitrate, 0.001 mM of erbium nitrate, 0.3 mM of lithium acetate and 2 mMs of citric acids are added in 8 milliliters of ethanol, are stirred 30 minutes；Then 2 mMs are added Basic zirconium chloride simultaneously stirs 30 minutes；Xerogel is obtained when insulation 2 is small at a temperature of 50 DEG C；By xerogel grind 30 minutes, so After be placed in Muffle furnace, in 700 DEG C insulation 4 it is small when, obtain final product after furnace cooling.
Embodiment 8
By 1.42 mMs of lutecium nitrates, 0.5 mM of ytterbium nitrate, 0.08 mM of europium nitrate, 0.001 mM of erbium nitrate, 0.4 mM of lithium acetate and 2 mMs of citric acids are added in 8 milliliters of ethanol, are stirred 30 minutes；Then 2 mMs are added Basic zirconium chloride simultaneously stirs 30 minutes；Xerogel is obtained when insulation 2 is small at a temperature of 50 DEG C；By xerogel grind 30 minutes, so After be placed in Muffle furnace, in 700 DEG C insulation 4 it is small when, obtain final product after furnace cooling.
Embodiment 9
50 grams of the luminescent material of embodiment 6 is weighed, with 150 grams of ink vehicles (phenolic resin oil 80 grams, alkyd resin oil 40 Gram, 30 grams of light resinon), appropriate amount of addition agent (8 grams of varnish, 0.5 gram of naphthoic acid cobalt) be mixed, rolled on three roller ink grinding mills System, prepares offset ink.Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, in 365nm, 395nm is with the excitation of 420nm xenon lamps, obtaining Eu3+Lower conversion red emission.
Embodiment 10
18% powder of stainless steel is added in the luminous anti-forgery ink of embodiment 9, according to known ink processing method, can be made into print Brush ink, except Er can be obtained under 980nm shooting conditions3+The upper conversion yellow emission of ion, in 365nm, 395nm with Under the excitation of 420nm xenon lamps, Eu is obtained3+Lower conversion red emission.

Claims (10)

  1. A kind of 1. Lu2Zr2O7System phosphor, it is characterised in that the molecule of the Lu2Zr2O7 system phosphors Formula is Yb/Eu/Er: Lu2Zr2O7, it is the doping of 10 ~ 30%, Eu for 1 ~ 10% using the molar percent wherein doping of Yb, The doping of Er is 0.001 ~ 0.01%；The Lu2Zr2O7System phosphor can obtain under 980nm shooting conditions To Er3+The upper conversion yellow emission of ion, under the excitation of 365nm, 395nm and 420nm xenon lamp, obtains Eu3+Lower conversion feux rouges Transmitting.
  2. A kind of 2. Lu according to claim 12Zr2O7System phosphor, it is characterised in that with molar percentage The doping that the meter doping that wherein doping of Yb is 15 ~ 25%, Eu is 3 ~ 8%, Er is 0.002 ~ 0.008%.
  3. A kind of 3. Lu according to claim 12Zr2O7System phosphor, it is characterised in that with molar percentage The doping that the meter doping that wherein doping of Yb is 18 ~ 22%, Eu is 4 ~ 6%, Er is 0.004 ~ 0.006%.
  4. 4. one kind prepares the Lu described in claim 1 ~ 3 any one item claim2Zr2O7The system of system phosphor Preparation Method, it is characterised in that this method comprises the following steps：
    1）Will（10-25）% mMs of lutecium nitrate,（2-9）% mMs of ytterbium nitrate,（0.5-4）% mMs of europium nitrate,（0.2- 0.5）% mMs of erbium nitrate, with（20-30）% mMs of citric acid is added to（4-10）In milliliter ethanol, stir 30-60 minutes Obtain clear solution A；
    2）Will（40-50）% mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；
    3）By 2）In solution exist（40-60）DEG C insulation（1-2）Hour, untill xerogel is obtained；
    4）By 3）Middle gained xerogel grinding（30-60）After minute, it is positioned in Muffle furnace, and（700-900）DEG C sintering（4- 8）Hour, obtain final product after furnace cooling.
  5. 5. the Lu2Zr2O7 system phosphors described in claim 1 ~ 3 any one item claim are prevented applied to optics Pseudo label material.
  6. 6. one kind Lu containing lithium2Zr2O7System phosphor, it is characterised in that the molecular formula of the phosphor is Yb/ Eu/Er/Li: Lu2Zr2O7, the doping using the molar percent wherein doping of Yb as 10 ~ 30%, Eu is 1 ~ 10%, Er's Doping is 0.0001 ~ 0.01%, and the doping of the Li is 10 ~ 30%；The phosphor excites bar in 980nm Er can be obtained under part3+The upper conversion yellow emission of ion, under the excitation of 365nm, 395nm and 420nm xenon lamp, obtains Eu3+'s Lower conversion red emission.
  7. 7. one kind Lu containing lithium according to claim 62Zr2O7System phosphor, it is characterised in that with moles hundred It is 3 ~ 8% to divide than the meter doping that wherein doping of Yb is 15 ~ 25%, Eu, and the doping of Er is 0.0002 ~ 0.008%, described Li doping be 15 ~ 25%.
  8. 8. one kind Lu containing lithium according to claim 62Zr2O7System phosphor, it is characterised in that with moles hundred It is 4 ~ 6% to divide than the meter doping that wherein doping of Yb is 18 ~ 22%, Eu, and the doping of Er is 0.0004 ~ 0.006%, described Li doping be 18 ~ 22%.
  9. 9. one kind prepares the Lu containing lithium described in claim 6 ~ 8 any one item claim2Zr2O7System phosphor Preparation method, it is characterised in that this method comprises the following steps：
    1）Will（10-25）% mMs of lutecium nitrate,（2-9）% mMs of ytterbium nitrate,（0.5-4）% mMs of europium nitrate,（0-0.5）% MM erbium nitrate, (5-10) % mMs of lithium acetate with（20-30）% mMs of citric acid is added to（4-10）Milliliter ethanol In, stirring obtains clear solution A in 30-60 minutes；
    2）Will（40-50）% mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；
    3）By 2）In solution exist（40-60）DEG C insulation（1-2）Hour, untill xerogel is obtained；
    4）By 3）Middle gained xerogel grinding（30-60）After minute, it is positioned in Muffle furnace, and（700-900）DEG C sintering（4- 8）Hour, obtain final product after furnace cooling.
  10. 10. the phosphor described in claim 6 ~ 8 any one item claim is applied to optical anti-counterfeiting label material.
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CN201711161443.9A CN107903898B (en) 2017-11-21 2017-11-21 A kind of Lu2Zr2O7System phosphor and preparation method thereof
CN201810754753.XA CN108659839A (en) 2017-11-21 2017-11-21 Phosphor is applied to optical anti-counterfeiting label material
CN201810754680.4A CN109021965A (en) 2017-11-21 2017-11-21 A kind of inorganic light-emitting device
CN201810754772.2A CN108624321A (en) 2017-11-21 2017-11-21 One kind Lu containing lithium2Zr2O7System phosphor
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