CN107828412B - A kind of blue long afterflow fluorescent powder and preparation method thereof - Google Patents

A kind of blue long afterflow fluorescent powder and preparation method thereof Download PDF

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Publication number
CN107828412B
CN107828412B CN201711061628.2A CN201711061628A CN107828412B CN 107828412 B CN107828412 B CN 107828412B CN 201711061628 A CN201711061628 A CN 201711061628A CN 107828412 B CN107828412 B CN 107828412B
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acid
long
fluorescent powder
blue
ester
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CN107828412A (en
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杨道救
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Ningbo Longer Lighting Co., Ltd.
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NINGBO LONGER LIGHTING CO Ltd
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Priority to CN201711061628.2A priority Critical patent/CN107828412B/en
Priority to CN201810787153.3A priority patent/CN108822606B/en
Priority to CN201810787106.9A priority patent/CN109097030A/en
Priority to CN201810787089.9A priority patent/CN109054815A/en
Priority to CN201810775671.3A priority patent/CN108753031A/en
Priority to CN201810775923.2A priority patent/CN108690607A/en
Publication of CN107828412A publication Critical patent/CN107828412A/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
    • C09K11/7792—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C09D11/50—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
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F13/00—Illuminated signs; Luminous advertising
    • G09F13/20—Illuminated signs; Luminous advertising with luminescent surfaces or parts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Abstract

The invention discloses a kind of blue long afterflow fluorescent powders and preparation method thereof, it is desirable to provide a kind of phosphor material powder with blue long afterflow luminescent properties belongs to phosphor technologies field.The chemical composition general formula of the fluorescent powder is Ca1‑x‑yAlO2Cl:xEu2+,yRe3+, wherein Re is Tm, and one or more of Gd and La are combined, and the value range of x and y are respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1.The centre of luminescence of the fluorescent powder is Eu2+Ion, by introducing Tm3+, Gd3+And La3+Equal rare earth impurities ion can effectively enhance its long afterglow effect.Long lad phosphor provided by the invention has the characteristics that chemical stability is good, after-glow brightness is high, persistence is long, can be used for safety instruction field.

Description

A kind of blue long afterflow fluorescent powder and preparation method thereof
Technical field
The invention belongs to phosphor technologies fields, more particularly to a kind of blue long afterflow fluorescent powder and preparation method thereof.
Background technique
Long-afterglow material is that one kind remains to after external stimulus (UV-visible light, X-ray, β ray etc.) stopping In considerable time (several seconds to ten more than hour) emit phosphorescence afterglow material long afterglow phenomenon before thousand in It is found in traditional Chinese Painting, and the scientific description in relation to long afterglow phenomenon can trace back to the 17th century still earliest, until 20th century, Science Report in relation to long afterglow is seldom always, and main cause has two o'clock, first is that long-persistence luminous intensity is lower, at that time weak Optical detector technology is difficult the very low twilight sunset of detected intensity；Second is that the afterglow intensity of long-afterglow material at that time is not high, Practical significance The landmark report of less related long-afterglow material research is derived from the text that Matszuzawa is delivered in August, 1996 Chapter, they have found, by long-afterglow material SrAl2O4: Eu2+In be co-doped with Dy3+, afterglow intensity can greatly enhance same with this When, it has also been found that codope Co can greatly improve afterglow intensity from this in ZnS:Cu, long-afterglow material is ground Takasaki etc. Study carefully and enters a new stage currently, long-afterglow material has been widely used in passive night mark and various has shown In track device
Currently, being concentrated mainly on blue-green luminous material for the research of long after glow luminous material, research system is mainly wrapped Include sulfide, aluminate and silicate etc..Early stage to sulfide systems is the study found that rare earth ion Dy3+And Tm3+Activation Sulfide can issue blue light.The long-afterglow material of aluminate-base plastidome largely shines in blue green light region, wherein preferably Blue long afterflow luminescent material be CaAl2O4: Eu2+, Nd3+, a length of 446nm of luminous spectrum spike, persistence can reach 1000min.In addition, using silicate as in the long after glow luminous material of matrix, related 2MOMgO2SiO2: Eu, Dy(M Alkali earth metal) research it is the most extensive, by the control to matrix components and Doped ions concentration, light emitting region can To cover green-yellow light from blue violet light.Wherein, that the long-afterglow material better performances of blue light-emitting is Sr2MgSi2O7: Eu2+, Dy3 +, emit main peak and be located at 469nm, persistence can be more than 10h, and luminescent properties are better than CaAl2O4: Eu2+, Nd3 +, and Sr2MgSi2O7: Eu2+, Dy3+With good chemical stability and thermal stability, high-purity silicon dioxide raw material valence It is honest and clean to be easy to get, therefore always by the attention of people.
Summary of the invention
In order to overcome a systems such as the luminous intensity of the above-mentioned material of blue long afterflow in the prior art is weaker, persistence is shorter Column problem, the present invention provides a kind of blue long afterflow fluorescent powder and preparation method thereof, the fluorescent powder have chemical stability it is good, The advantages that after-glow brightness is high, persistence is long can be used for the fields such as decoration, emergency display.
To solve above-mentioned the deficiencies in the prior art, the technical solution adopted in the present invention is as follows:
A kind of blue long afterflow fluorescent powder, the chemical composition general formula of the fluorescent powder are Ca1-x-yAlO2Cl: xEu2+,yRe3+, wherein Re is Tm, and one or more of Gd and La are combined, and the value range of x and y are respectively as follows: 0.01≤x≤0.1, 0.01≤y≤0.1.Preferably, the centre of luminescence of the fluorescent powder is Eu2+Ion, by introducing rare earth ion Tm3+、Gd3+ And La3+One or more of combination provide trap level, effectively enhance long-persistence luminous effect.
A kind of preparation method of blue long afterflow fluorescent powder, it is characterised in that the following steps are included:
(1) ingredient: with the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3、Tm2O3、Gd2O3And La2O3As raw material, according to Chemical composition general formula Ca1-x-yAlO2Cl: xEu2+, yRe3+The proportion of middle each element accurately weighs each raw material；
(2) mixing: above-mentioned raw materials are put into agate mortar, and to carry out ground and mixed uniform, according to total mass ratio 1:1 when grinding Dehydrated alcohol is added as abrasive media, milling time is 0.5 ~ 1 hour；
(3) it dries: the pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours under the conditions of 80 DEG C, Sample and grinding distribution are taken out after the completion of dry, obtain uniformly mixed raw material；
(4) it is sintered: the uniformly mixed raw material being put into high temperature process furnances and is pre-sintered, sintering temperature 1000 ~ 1300 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 7.5 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixing Gas cools to room temperature with the furnace after the completion of sintering, obtain sintered body；
(5) select powder: the sintered body that step (4) are obtained carries out ball mill grinding, and using gas flow sizing machine to smashed Powder is classified according to particle size to get the blue long afterflow fluorescent powder.
Compared with prior art, the beneficial effects of the present invention are:
(1) the present invention provides a kind of novel blue long lad phosphor, matrix group becomes CaAlO2Cl passes through rare earth Ion Eu2+Doping obtains blue emission, by introducing rare earth ion Tm3+、Gd3+And La3+One or more of combination provide Trap level effectively enhances after-glow brightness and the time of the fluorescent powder；
(2) blue long afterflow fluorescent powder provided by the invention is with chemical stability is good, after-glow brightness is high, persistence is long The advantages that.
The invention also discloses a kind of blue long afterflow light-emitting components, using made of above-mentioned blue long afterflow fluorescent powder Substrate.
The invention also discloses a kind of blue long afterflow light-emitting components, including substrate and the long afterglow being attached in substrate hair Optical thin film, the long-persistence luminous film are that above-mentioned blue long afterflow phosphor powder or blue long afterflow fluorescent powder are thin Piece.
It include substrate and the long afterglow being attached in substrate hair the invention also discloses a kind of blue long afterflow light-emitting component Optical thin film, the long-persistence luminous film are blue long afterflow phosphor powder or blue long afterflow fluorescent powder thin slice.
Preferably, long-persistence luminous film with a thickness of 1-10mm.
Substrate of the invention can be rigid basement, or flexible substrates.Preferably, the rigid basement can To be selected from glass, silicon, steel, ceramics, cement, timber and stone, the flexible substrates can be selected from PDMS (polydimethylsiloxanes Alkane) film, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimides) film With PVA (polyvinyl alcohol) film.
Above-mentioned blue long afterflow light-emitting component preparation method, comprising: by blue long afterflow phosphor as described above The suspension of last particle is coated in substrate as described above.
Although by suspension is prepared into blue long afterflow phosphor powder particle suspension liquid solvent as described above, then Coated on can be prepared in the substrate meet the present invention claims light-emitting component, but also contain high score in the suspension When sub- substance, the sensitivity of final prepared light-emitting component and precision can be promoted further.
The content of the blue long afterflow phosphor powder particle can also change in a wider scope, preferable case Under, the suspension based on 100 parts by weight, the content of the blue long afterflow phosphor powder particle is 0.5-10 weight Part, 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 of glue, carboxymethyl starch, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose are a variety of.
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, 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 of butanone, repefral and D-sorbite are a variety of.
According to the present invention, the suspension of the blue long afterflow phosphor powder particle is coated on the substrate surface Method can be the selection of this field routine, for example, can also use and print using the coating methods such as spraying, spin coating Technology.The suspension of blue long afterflow phosphor powder particle is imprinted on the surface of substrate to the present invention by preferred printing technique herein On, so that the sensitivity for the sensor being prepared and precision are further promoted.Wherein, the printing technique can Selected from one of dispensing, inkjet printing, water transfer, silk-screen printing and roll-to-roll printing.When use printing technique will be described When the suspension of blue long afterflow phosphor powder particle is printed on the surface of the substrate, the suspension is preferably prepared into ink Water, the preparation method of the ink are by obtaining the suspension blending and stirring or blending ultrasonic disperse.
The invention also discloses a kind of blue long afterflow light-emitting component, which includes macromolecule material Material and the blue long afterflow phosphor powder, blue long afterflow phosphor powder are evenly distributed in high molecular material, blue The additional amount of color long lad phosphor powder is 1 ~ 90%；Preferably 10 ~ 80%.High molecular material can be selected from PDMS (poly- diformazan Radical siloxane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimides) and PVA (polyvinyl alcohol) is thin.Appropriateness in order to improve the performance of processing, which can also be added coupling agent, lubricant, plasticising Agent etc..
The invention also discloses a kind of ink, which includes ink conventional ingredient and the blue long afterflow fluorescent powder Powder, blue long afterflow phosphor powder are evenly distributed in ink conventional ingredient, the addition of blue long afterflow phosphor powder Amount is 1 ~ 30%；Preferably 5 ~ 10%.Ink resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil-based ink is also possible to water-based ink.
The invention also discloses a kind of coating, which includes coating conventional ingredient and the blue long afterflow fluorescent powder Powder, blue long afterflow phosphor powder are evenly distributed in coating conventional ingredient, the addition of blue long afterflow phosphor powder Amount is 1 ~ 30%；Preferably 5 ~ 10%.Coating resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil paint is also possible to water paint.
In addition, by the way that common paper, synthetic paper or epoxy resin, poly- second will be formed in comprising blue long afterflow fluorescent powder The macromolecules such as alkene, polyethylene terephthalate, polyester, polypropylene, polyvinyl chloride raw material, natural rubber or synthesis rubber Glue, glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete or their combination and their fabricated product Deng exterior trim surface, or by inside contain blue long afterflow fluorescent powder.
Blue long afterflow light-emitting component of the present invention can be used as illumination, for safety display utilization.Such as are as follows: device Vibrate the luminaires such as lamp, wind power lamp；Promptly, abnormal notification, very apparatus, dangerous display, very lamp, non-common mark, rescue Mark, signboard, the display device of life tool；Safety guard hangs on nervous rope, animal protective fence around shop building； Use filament to the pedal of ladder, handrail and the mesh that is arranged in the state ofs being partly embedded in road etc.；Health promoting appliance, walking are auxiliary Help utensil (walking auxiliary walking stick, the notification that shines antenna etc.)；The jewellery such as earrings, necklace；Support cutting for pillar, railway of flag etc. The exterior trim component or build-in components of the road road Ji Jie stick, bicycle, automobile, electric car, ship, aircraft etc., fishing tackle (simulation Bait, fishing rod, fishing net etc.；Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy (float, buoy)； The position of the domestic animals such as the pets such as people, dog, cat, ox, pig, sheep, chicken etc. is shown；Fan (blade etc. of wind-power electricity generation, ventilating fan etc.), Clothes (shoes, gym suit, manually shine cloth, artificial luminous filament, artificial luminescent fibre etc.)；Pack (case, bracket, device, letter Envelope, ground paper, crust packaging, external overlay film), medical products (breathing assistance utensil, experimental study equipment) robot it is (artificial to shine Hair structure body, artificial shiny skin, manually shine body) etc..It is covered as coating composition, ink composition, cement, surface Utilization example containing blue long afterflow fluorescent powder in lid agent, can enumerate: financial institution, community organization, credit card company, circulation The mail pieces such as the crimping postcard sheet material used in industry etc., in the bonding agent of stickup containing blue long afterflow fluorescent powder； The furniture such as chair, bed；Flooring material, ceramic tile, wall material, prefabricated board material, paveio(u)r, timber steel concrete etc. Building materials；It is equipped on the automated navigation system device of vehicle；For operating the operating device of audio devices and air-conditioning etc.；Household electrical appliances system The input units such as product, portable machine, electronic computer；The storage of the images such as digital camera, CCD camera, film, photo, image Means etc..
It can produce new appearance and making blue long afterflow light-emitting phosphor, therefore also consider to toy, movable quotient The expansion of the amusement commodity, daily necessity such as product.For example: it is the wind long narrow flag such as dynamic toy, kite, carp shape flag, swing, fast Ski-running driving, carrousel, bow and arrow etc.；Pass through wind-force while the Powerless type light emitting device (windbell etc.) of generation sound and light.Hair The windmill of photosphere (golf, the ball of baseball, table tennis ball, ball of billiard ball etc.), luminous mechanism；Balloon；Laminated structure object For paper, batch flute, paper folding, paper balloon, folding fan, New Year card, draw this；(jumping pole, fencing, bow and arrow are isometric for sporting goods Size objects etc.)；The score confirmation pressure sensitive sealant part of golf club, dynamic ornamentation body, moves tennis court line tester State engraving, dynamic souvenir；Dynamic Display device；Luminous decorative device；The audio device such as loudspeaker, musical instrument (violin, guitar The diaphragms such as wind instruments, the glass such as percussion instruments, trumpet, the flutes such as equal stringed musical instruments, xylophone, drum), tuning fork etc.；The joy such as lipuid goods Happy commodity；The water plant of the ornamental sink in aquarium etc., container；Luminous wrist watch, luminous sand timer or sand timer type shine Device；Light emitting-type simulates candle device；The artificial plant that can be shone；Artificial eye；Cosmetics group containing adhesion polymer Conjunction object, the printed article and marketable securities, the printer's ink containing long-persistence luminous particle, ticket that forgery can be distinguished under visual state According to, the admission of check, stock, bond, various security, exchange ticket, books certificate, the ticket of traffic organization, toll facility, project Middle lottery ticket of ballot certificate that certificate, lottery ticket, Public Physical Education are competed etc., bank note, identity card, ticket, the pass etc., passport, writing are organic The printed article of ciphertext book seals sealing element etc..
Using shining along with long lad phosphor, keep the photochemical catalyst for being attached to blue long afterflow phosphor surface living Obtained from change, long-lasting phosphor-photochemical catalyst complex can be used for: antibacterial, sterilization, the treatment to non-human animal, vehicle The dirt purifications of the antibacterial articles such as handrail, handle, the fluid of internal wall surface such as utilize the piping for being located at dark place The purification of energy of flow.Long-lag phosphor activates the photocrosslinking agent in macromolecule resin, can also promote by shining Crosslinking.
By the way that blue long afterflow fluorescent powder of the invention with being mixed in resin, can be formed resin combination of the invention Object.
In addition, being formed again by the way that other inorganic material or organic material are further added in resin combination of the invention Condensation material can also form long-lasting phosphor of the 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 blue long afterflow fluorescent powder is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to tree 100 mass parts of rouge are compounded above-mentioned 30~300 mass parts of blue long afterflow fluorescent powder.Blend can be by using tapered mixing The mixing machines such as machine, V-Mixer, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill make resin Composition.
In addition, in the case where forming long-lasting phosphor by the resin combination, such as obtain the long-persistence luminous of sheet When body, such as relative to 100 parts by weight of Corvic, be compounded above-mentioned 50~200 mass parts of blue long afterflow fluorescent powder, Calcium -3~5 mass parts of zinc system stabilizer, 30~100 mass parts of dioctyl phthalate as plasticizer, are existed with two-roller mill It is kneaded at 150~200 DEG C, so as to obtain the long-lasting phosphor with flexible sheet.
When obtaining the long-lasting phosphor of film-form, such as relative to 100 mass of pet resin Part, above-mentioned 20~50 mass parts of blue long afterflow fluorescent powder are compounded, with double screw extruder, inflation processing machine at 250~300 DEG C Under be kneaded, formed, so as to obtain the long-lasting phosphor of film-form.
When obtaining the long-lasting phosphor of other shapes, such as relative to 100 mass parts of acrylic resin, it is long to be compounded blue 5~100 mass parts of persistence phosphor are kneaded at 170~200 DEG C with double screw extruder, are formed, so as to obtain Band-like, plate, rodlike, partical long-lasting phosphor.In addition, by using injection (mo(u)lding) machine to grain at 170~200 DEG C Expect that the long-lasting phosphor of shape carries out machine-shaping, the long-lasting phosphor of available three-dimensional shape.
It 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), gather alkenyl aroma hydroxy-aromatic resin The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polylactic acid, bisphenol-A Be the polycarbonate such as polycarbonate, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, The polyacrylic acid such as polyacrylonitrile, polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, gather at styrene-acrylonitrile copolymer (AS resin) Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, liquid crystal polymer ethylene and propylene copolymer, ethylene or propylene With copolymer, ethylene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylene, 1- hexene, 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 It can be the copolymer of any forms such as random copolymer, block copolymer when object.As thermosetting resin, can enumerate: phenol Urea formaldehyde, urea resin, melamine resin, 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 light, the resin of radiation curing.
In turn, it can enumerate: natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethylene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
It in addition to this, can be by pigment, dyestuff, lubricant, antioxidant, ultraviolet absorbing agent, light stabilizer, antistatic Agent, fire retardant, fungicide, antibacterial agent, solidification catalyst, Photoepolymerizationinitiater initiater etc. and blue long afterflow fluorescent powder of the invention It is mixed together, is shaped to rodlike, plate, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gel, 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, the glass flake, holographic pigment covered by titanium oxide, iron oxide Deng.In addition to this, it 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.
It 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 system azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purples face such as cobalt violet, quinacridone violet, dioxazine violet 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 dye, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
It as antioxidant, can enumerate: hindered phenolic compound, phosphite ester based compound, phosphinate system chemical combination Object and thioether based compound etc..
It as hindered phenolic compound, can enumerate: alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyls -3 ', 5 '-di-tert-butyl-phenyls) propionic ester, 2- tert-butyl -6- (3 '-tert-butyls -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyl acrylate, 2,6- di-t-butyl -4- (N, N- dimethylaminomethyl) phenol, bis- uncle of 3,5- Butyl -4- benzylphosphonic acid diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl -6- tert-butyl phenol), 4,4 '-methylene-bis(2,6-di-t-butyl phenol)s, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylenes-bis- (6- Alpha-Methyl-benzyl-paracresol) 2,2 '-ethidines-bis- (4,6- di-t-butyl Phenol), 2,2 '-butanes-bis- (4- methyl-6-tert-butylphenol), 4,4 '-butanes bis- (3 methy 6 tert butyl phenols), Triethylene glycol-N- double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters, bis- [3- (the tertiary fourths of 3,5- bis- of 1,6-HD Base -4- hydroxy phenyl) propionic ester], bis- [2- tert-butyl -4- methyl 6- (3- tert-butyl -5- methyl -2- hydroxybenzyl) phenyl] it is right Bis- { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propiono the oxygroup] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (6- tert-butyl-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenol), bis- (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- Thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], bis- (just pungent sulfenyl) -6- (4- hydroxyls of 2,4- Base -3 ', 5 '-di-tert-butyl amidos) -1,3,5- triazine, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy group Cinnamamide), N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hydrazines of N ' -, (2- methyl -4- hydroxyl of 1,1,3- tri- Base -5- tert-butyl-phenyl) butane, 1,3,5- trimethyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid esters, 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono oxygroup] 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-phenyl) ester, phosphorous acid three (2,6- di-tert-butyl-phenyl) ester, two Stearyl pentaerythritol diphosphites, bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, bis- (tertiary fourths of 2,6- bis- Base -4- aminomethyl phenyl) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyl) pentaerythrite diphosphorous acids Ester, bis- { bis- (1- methyl-1-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, bis- (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..As other Phosphite ester based compound can be enumerated and be reacted with dihydric phenol class 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 are sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyl) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylens, four (2,6- di-tert-butyl-phenyl) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylens, the sub- phosphine of four (2,6- di-tert-butyl-phenyl) -3,3 '-biphenylene two Acid esters, bis- (2,4- di-tert-butyl-phenyl) -4- phenyl-phenyl phosphinates, bis- (2,4- di-tert-butyl-phenyl) -3- phenyl-benzene Base phosphinate, bis- (2,6- di-n-butyl phenyl) -3- phenyl-phenyl phosphinates, bis- (2,6- di-tert-butyl-phenyl) -4- benzene Base-phenylphosphite ester and bis- (2,6- di-tert-butyl-phenyl) -3- phenyl-phenyl phosphinates etc..
It 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 acid of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionate), pentaerythrite-four (3- octadecyl thiopropionate), season penta Tetrol four (3- myristyl thiopropionate) and pentaerythrite-four (3- stearyl-thio propionic ester) etc..As comprising ultraviolet The light stabilizer of light absorbers can be enumerated: 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..
It as benzophenone based compound, can enumerate: benzophenone, 2,4-DihydroxyBenzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenones, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyl benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -5- sulphur Acyl group benzophenone, 5- chlorine-2-hydroxyl benzophenone, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -2 ' - Carboxyl benzophenone and 2- hydroxyl -4- (2- hydroxy-3-methyl-acryloxy isopropoxy) benzophenone etc..
It as benzotriazole based compound, can enumerate: 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- (3,5- bis- Tert-butyl -2- hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) benzotriazole, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) -5- chlorobenzotriazole, 2- (5- tert-butyl -2- hydroxy phenyl) benzotriazole, 2- [2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyls -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 Salicylic acids alkyl phenyl esters such as phenylester etc..
It as oxanilide based compound, can enumerate: 2- ethyoxyl -2 '-ethyloxanilide, 2- ethyoxyl -5- Tert-butyl -2 '-ethyloxanilide and 2- ethyoxyl -3 '-dodecyl butoxanilide etc..
It as cyanoacrylate based compound, can enumerate: cyano -3 ethyl -2-, 3 '-diphenylacrylate esters, 2- Ethylhexyl-cyano -3,3 '-diphenylacrylate ester etc..
It as the amine compound that is obstructed, can enumerate: 4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl keto Base -2,2,6,6- tetramethyl piperidine, 4- acryloxy -2,2,6,6- tetramethyl piperidine, 4- (phenylacetyl oxygroup) -2,2,6, 6- tetramethyl piperidine, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidine, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl oxygroup -2,2,6,6- tetramethyl piperidine, 4- benzyl oxygroup -2,2, 6,6- tetramethyl piperidine, 4- phenoxy group -2,2,6,6- tetramethyl piperidine, 4- (ethylcarbamoyl oxygroup) -2,2,6,6- tetramethyl Phenylpiperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidine, 4- (phenylcarbamoyl oxygroup) -2,2,6, 6- tetramethyl piperidine, bis- (2,2,6,6- tetramethyl -4- piperidyl) carbonic esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Bis- (2,2,6,6- tetramethyl -4- piperidyl) adipate esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) terephthalates, 1,2- bis- (2,2,6,6- tetramethyl -4- piperidyl oxygroup)-ethane, α, the bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen of α ' - Base)-paraxylene, bis- (2,2,6,6- tetramethyl -4- piperidyl)-toluylene -2,4- diurethanes, it is bis- (2,2, 6,6- tetramethyl -4- piperidyl)-hexa-methylene -1,6- diurethane, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic ester, three (2,2,6,6- tetramethyl -4- piperidyl)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono oxygroup } -2,2,6,6- tetramethyl piperidine and 1,2,3,4- butane tetracarboxylic acid and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidine and β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiro (5,5) of 2,4,8,10- 11 Alkane] dimethanol condensation product etc..
As antistatic agent, can enumerate: the toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are multiple 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 agent such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-laurel Amide propiono) the quaternary ammonium salts system, sulfonate based compound, alkyl phosphate such as trimethyl ammonium sulfate, neopelex The antistatic agent etc. of the organic systems such as based compound.
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 type epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, using brominated bisphenol A as the polycarbonate oligomer of Material synthesis, two phthalimide chemical combination of bromination The compounds such as the brominated diphenyls base alkane such as object, 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, bis- (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethylene-is bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
It 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 naphthalene ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyl) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyl phosphate ester acid, 2- methacryloxyethyl phosphate ester acid, diphenyl -2- acryloyl Oxygroup ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyl 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- phenylene bis- (2,6- dimethylphenylphosphates), resorcinol 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 condensations phosphate such as phosphate and their condensation product etc..
It as chlorine-based flame retardant, can enumerate: five cyclodecane of pentachloro-, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..It as triazine flame retardant, can enumerate: melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- Diamino -6- nonyl -1,3,5- triazine, 2,4- diamino -6- hydroxyl -1,3,5- triazine, dihydroxy -1,3 2- amino -4,6-, 5- triazine, 2,4- diamino -6- methoxyl group -1,3,5- triazine, 2,4- diamino -6- ethyoxyl -1,3,5- triazine, 2,4- diamino Base -6- propoxyl group -1,3,5- triazine, 2,4- diamino -6- isopropoxy -1,3,5- triazine, sulfydryl -1 2,4- diamino -6-, 3,5- triazine and 2- amino -4,6- dimercapto -1,3,5- triazine etc..
It as the salt of phosphoric acid and 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 organochlorines such as machine thiophanate fungicide, captan, Bravo system fungicide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximides system such as benzimidazole system fungicide, iprodione, vinclozolin, procymidone fungicide, furametpyr The morpholines system fungicide such as the phenylpyrroles such as amine system fungicide, fludioxonil system fungicide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidines system fungicide such as the methoxy acrylates 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 Bis- (acetyl bromide oxygroup) ethane of amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2-, cinnamic acid, acetic acid benzene Ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, the bromo- 3- itrile group propionyl of 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
It as antibacterial agent, can enumerate: make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Close inorganic system's powder obtained from object.It as load, can enumerate: zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..In addition it can enumerate: with phosphate, boric acid system, silicic acid system Be respectively in one kind or two or more glass as glass forming constituents of glass containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate: fatty acid, fatty acid metal salts, oxo fatty acid, paraffin, low molecular weight it is poly- Alkene, fatty acid amide, alkylenebisfatty amide, aliphatic ketone, fatty acid part are saponified ester, fatty acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethyl alcohol ester and modified organic silicon etc..
As fatty acid, can enumerate: oleic acid, stearic acid, lauric acid, hydroxy stearic acid, behenic acid, arachidonic acid, The fatty acid of the carbon numbers 6~40 such as linoleic acid, linolenic acid, ricinoleic acid, palmitinic acid, montanic acid and their mixture.As rouge Fat acid metal salt can be enumerated: 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 acid Alkali (soil) gold of the fatty acid of carbon numbers 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acid barium, montanic acid sodium and montanic acid calcium Belong to salt.
It as oxo fatty acid, can enumerate: 1,2- stearoxylic acid etc..
It as paraffin, can enumerate: the paraffin of 18 or more the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline.
It as the polyolefin of low molecular weight, can enumerate: polyethylene wax, maleic acid modified polyethylene wax, the poly- second of oxidized form Alkene wax, haloflex wax and the polyolefin below of polypropylene wax equimolecular quantity 5000.It, specifically can be with as fatty acid amide It enumerates: the fatty acid amide of 6 or more the carbon numbers such as oleamide, erucic amide, Shan Yu amide.
It as alkylenebisfatty amide, can enumerate: methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty amide of 6 or more the carbon numbers such as bis- (2- hydroxyethyl) stearmides.
It as aliphatic ketone, can enumerate: the aliphatic ketone of 6 or more the carbon numbers such as higher aliphatic ketone.As fatty acid moieties Divide saponification ester, can enumerate: partly-hydrolysed ester of montanic acid etc..
It as fatty acid low-carbon-ester, can enumerate: stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acid ester, arachidonate, montanate and isostearate etc..
It 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 ester etc..
As fatty acid polyglycol ethyl alcohol 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 contains Having organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness of higher fatty acids has Machine silicon etc..
It as solidification catalyst, can enumerate: (peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and the organic peroxides, octyl acid tin, 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 fatty acid salt, 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 amines, 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..In turn, it can enumerate: single (2- (methyl) acryloxy second Base) phosphate cpds, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
It as Photoepolymerizationinitiater initiater, can enumerate: (2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propane - 1- ketone, 1- hydroxycyclohexylphenylketone, 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 oxide etc.) and benzil dimethyl ketal etc..
In turn, by the way that length of the invention can also be made with coating is mixed in blue long afterflow fluorescent powder of the invention Afterglow coating composition.
Long-persistence luminous property coating composition of the invention can be coated with the surface of other materials.
In addition, the hair of the long-persistence luminous property coating composition of the invention containing blue long afterflow fluorescent powder of the invention Brightness is high, therefore can carry out visual high coating.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root According to need can also contain: solvent, dispersing agent, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoaming agent, The coating such as antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and antibacterial agent Use additive.
As material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet light also can 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..
It as ink film forming material, can enumerate: polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
It 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 (single ethyl of C4~10, such as tetrahydrofuran, EG Ether, the single-butyl ether of EG, the monomethyl ether of PG and DEG single ethylether), (C3~10, such as methyl iso-butyl ketone (MIBK), two are just for ketone Butyl ketone), alcohol (C1~10, such as methanol, ethyl alcohol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohol), amide (C3~6, such as dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone), sulfoxide (C2~4, such as dimethyl sulfoxide) and their mixed solvent of more than two kinds, water or aforementioned mixed solvent.As dispersion Agent can enumerate: the formal of naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] as long as being macromolecule dispersing agent Woods condensation product, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2~4) carboxylic acid (Malaysia Acid/glycerol/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~10000) and polyethylene Alcohol (Mn2000~100000) etc..
As low molecule dispersing agent, 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) 1~30 mole of addition product of AO (C2~4) of amide.
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 fatty acid (lauric acid, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, sorb Sugar alcohol and anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the fatty acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulphur of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 Acid esters 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 list of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 The salt [alkali metal (same as described above) salt, quaternary ammonium salt etc.] of phosphate or bisphosphate.
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and tertiary amine (the dimethyl stearyl of C4~30 Amine etc.)] inorganic acid (hydrochloric acid, sulfuric acid, the nitre of the monoesters of hydrochloride, triethanolamine and the fatty acid of C4~30 (same as described above) Acid and phosphoric acid etc.) salt.
(8) quaternary
The nothing of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 Machine acid (same as described above) salt etc..
It as inorganic dispersant, can enumerate: alkali metal (same as described above) salt and phosphate dispersing agent (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
It as filler, can enumerate: 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 substances based inorganic material such as object, silicon carbide, silicon nitride.Separately Outside, the metal powders such as aluminium, zinc, copper can also be added depending on the application.In turn, it as the concrete example of filler, can enumerate: dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based substance；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 substances based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, silicon carbide, 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 powders such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Equal carbon body etc..
It as thickener, can enumerate: montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic fillers 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 epoxy-modified object of polyethers The association thickeners such as rouge system thickener, urethane-modified polyether system, polyurethane resin system of polyether polyol system etc. are special The eggs such as the surfactants 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 type 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 At object, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
Curing agent can be enumerated as the curing agent of polyalcohols: 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 body of polyisocyanate compound, buret body, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propylene glycol, 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. It like that at normal temperature being capable of cured isocyanates.It as the curing agent of epoxy resin, can enumerate: acid anhydrides, phenolic aldehyde tree Rouge, polyamide, amine additives, urea resin, melamine resin and isocyanates etc..
It as crosslinking agent, can enumerate: melamine resin, urea resin, polyisocyanate compound, block polyisocyanate cyanogen Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Rouge 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..
It as pigment, other than aforesaid pigments, can also enumerate: vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Equal vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid object, one hydrogen magnesium of phosphoric acid, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid object, phosphorus Sour magnesium cobalt eutectoid object, magnesium phosphate nickel eutectoid object, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid object, 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 object；The rust resisting pigment containing zinc ingredient 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 ingredient or calcium metasilicate ingredient；Calcium from The metal ion exchangeds silica such as son exchange silica, magnesium ion exchange silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoaming agent, for example: silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness are poly- The organic silicon-types such as siloxanes defoaming agent, mineral oil system defoaming agent, non-organic silicon polymer system defoaming agent, comprising changing selected from organic At least one kind of defoaming agent in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol comprising 18 or more carbon number Defoaming agent etc..
For antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and Antibacterial agent etc. can enumerate aforementioned substances.
Detailed description of the invention
Fig. 1 provides the excitation and emission spectra of 1 ~ 3 sample of embodiment for the present invention；
Fig. 2 provides the after-glow light spectrogram of 1 ~ 3 sample of embodiment for the present invention；
Fig. 3 provides the after-glow light spectrogram of 4 ~ 6 sample of embodiment for the present invention.
Specific embodiment
Invention is further described in detail for 1-3 and specific embodiment with reference to the accompanying drawing.
Embodiment 1
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.96AlO2Cl: 0.02Eu2+, 0.02Tm3+。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3And Tm2O3As raw material, according to chemical composition Ca0.96AlO2Cl: 0.02Eu2+, 0.02Tm3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into agate It is uniform that mortar carries out ground and mixed, dehydrated alcohol is added as abrasive media according to total mass ratio 1:1 when grinding, milling time is 0.5 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is pre-sintered, sintering temperature is 1300 DEG C, and sintering time is 4 hours, and heating rate is 7.5 DEG C/min, sintering atmosphere 5% H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；The sintered body of acquisition is subjected to ball It is milled broken, and smashed powder is classified according to particle size to get the blue long afterflow using gas flow sizing machine Fluorescent powder.
Embodiment 2
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.98AlO2Cl: 0.01Eu2+, 0.01Gd3+。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3And Gd2O3As raw material, according to chemical composition Ca0.98AlO2Cl: 0.01Eu2+, 0.01Gd3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into agate It is uniform that mortar carries out ground and mixed, dehydrated alcohol is added as abrasive media according to total mass ratio 1:1 when grinding, milling time is 0.5 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is pre-sintered, sintering temperature is 1300 DEG C, and sintering time is 5 hours, and heating rate is 7.5 DEG C/min, sintering atmosphere 5% H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；The sintered body of acquisition is subjected to ball It is milled broken, and smashed powder is classified according to particle size to get the blue long afterflow using gas flow sizing machine Fluorescent powder.
Embodiment 3
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.94AlO2Cl: 0.04Eu2+, 0.02La3+。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3And La2O3As raw material, according to chemical composition Ca0.94AlO2Cl: 0.04Eu2+, 0.02La3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into agate It is uniform that mortar carries out ground and mixed, dehydrated alcohol is added as abrasive media according to total mass ratio 1:1 when grinding, milling time is 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours under the conditions of 80 DEG C, after the completion of dry Sample and grinding distribution are taken out, uniformly mixed raw material is obtained；By the uniformly mixed raw material be put into high temperature process furnances into Row is pre-sintered, and sintering temperature is 1100 DEG C, and sintering time is 6 hours, and heating rate is 7.5 DEG C/min, sintering atmosphere 5%H2/ 95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；The sintered body of acquisition is subjected to ball milling It crushes, and using gas flow sizing machine smashed powder is classified according to particle size glimmering to get the blue long afterflow Light powder.
Embodiment 4
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.84AlO2Cl: 0.08Eu2+, 0.04Tm3+, 0.04Gd3 +。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3、Tm2O3And Gd2O3As raw material, according to chemical composition Ca0.84AlO2Cl: 0.08Eu2+, 0.04Tm3+, 0.04Gd3+The proportion of middle each element accurately weighs each raw material；By above-mentioned original Material is put into agate mortar, and to carry out ground and mixed uniform, dehydrated alcohol is added as abrasive media according to total mass ratio 1:1 when grinding, Milling time is 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours under the conditions of 80 DEG C, Sample and grinding distribution are taken out after the completion of dry, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature It is pre-sintered in tube furnace, sintering temperature is 1100 DEG C, and sintering time is 5 hours, and heating rate is 7.5 DEG C/min, sintering Atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the sintering of acquisition Body carries out ball mill grinding, and is classified using gas flow sizing machine to smashed powder according to particle size to get the indigo plant Color long lad phosphor.
Embodiment 5
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.88AlO2Cl: 0.06Eu2+, 0.03Gd3+, 0.03La3 +。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3、Gd2O3And La2O3As raw material, according to chemical composition Ca0.88AlO2Cl: 0.06Eu2+, 0.03Gd3+, 0.03La3+The proportion of middle each element accurately weighs each raw material；By above-mentioned original Material is put into agate mortar, and to carry out ground and mixed uniform, dehydrated alcohol is added as abrasive media according to total mass ratio 1:1 when grinding, Milling time is 0.5 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 is small under the conditions of 80 DEG C When, sample and grinding distribution are taken out after the completion of dry, obtains uniformly mixed raw material；The uniformly mixed raw material is put into height It is pre-sintered in warm tube furnace, sintering temperature is 1200 DEG C, and sintering time is 5 hours, and heating rate is 7.5 DEG C/min, is burnt Knot atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the burning of acquisition Knot body carries out ball mill grinding, and is classified using gas flow sizing machine to smashed powder according to particle size to get described Blue long afterflow fluorescent powder.
Embodiment 6
A kind of blue long afterflow fluorescent powder, chemical composition Ca0.8AlO2Cl: 0.1Eu2+, 0.04Tm3+, 0.04Gd3+, 0.02La3+。
With the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3、Tm2O3、Gd2O3And La2O3As raw material, according to chemical composition Ca0.8AlO2Cl: 0.1Eu2+, 0.04Tm3+, 0.04Gd3+, 0.02La3+The proportion of middle each element accurately weighs each raw material； Above-mentioned raw materials are put into agate mortar, and to carry out ground and mixed uniform, and dehydrated alcohol conduct is added according to total mass ratio 1:1 when grinding Abrasive media, milling time are 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, is kept the temperature under the conditions of 80 DEG C Drying 4 hours takes out sample and grinding distribution after the completion of dry, obtains uniformly mixed raw material；By the uniformly mixed original Material, which is put into high temperature process furnances, to be pre-sintered, and sintering temperature is 1200 DEG C, and sintering time is 4 hours, heating rate 7.5 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；It will The sintered body of acquisition carries out ball mill grinding, and is classified to smashed powder according to particle size using gas flow sizing machine, Up to the blue long afterflow fluorescent powder.
Fig. 1 provides the excitation and emission spectra of 1 ~ 3 sample of embodiment for the present invention, and left-most curve is excitation spectrum in figure, Monitoring wavelength is 448nm, and the right curve is emission spectrum, excitation wavelength 275nm, it can be seen from the figure that the sample in figure The wave-length coverage that can be effectively excited is the region black light (200 ~ 350nm), and the peak wavelength of emission spectrum is located at 448nm's Blue region, the centre of luminescence are divalent Eu2+Ion；Fig. 2 and Fig. 3 is respectively the twilight sunset spectrum of embodiment 1 ~ 3 and embodiment 4 ~ 6 Figure, it can be seen from the figure that active ions Eu2+With impurity energy level ion Tm3+、Gd3+And La3+Doping concentration to sample just Beginning fluorescence intensity and afterglow intensity and persistence by great influence, pass through introducing rare earth ion Tm3+、Gd3+And La3+In One or more combination provides trap level, can effectively enhance after-glow brightness, extend persistence.
Since the 1990s, with Eu2+The alkaline earth aluminate of activation is shining for the long after glow luminous material of representative Mechanism does not understand long-persistence luminous mechanism at present though always being the hot spot of research completely, has at least obtained following total Know: (1) adulterating Eu2+It is the centre of luminescence；(2) various defects present in crystal have important influence with twilight sunset to luminous；(3) Codope trivalent rare earth ions RE3+Addition produce more defect levels；(4) when exciting the electrons and holes that generate respectively by Electron trap and hole trap capture；(5) electronics or hole that trap captures under thermal agitation release at the appropriate speed； (6) the composite guide photoluminescence of electrons and holes is during actual development, since the type of long after glow luminous material is more, no Same material has different luminous mechanisms, and the luminescence mechanism of some materials is also not clear at present, and therefore, it is suitable to seek Matrix and active ions are most important for the exploitation of new type long-persistence material.Further, since the preparation of long after glow luminous material Method is more, and there are respective advantage and disadvantage, therefore the optimum organization of the preparation method to various long after glow luminous material Very crucial effect will be played to the popularization and application of long after glow luminous material.

Claims (2)

1. a kind of blue long afterflow fluorescent powder, which is characterized in that the chemical composition general formula of the fluorescent powder is Ca1-x-yAlO2Cl:xEu2+, yRe3+, wherein Re is Tm, and one or more of Gd and La are combined, and the value range of x and y are respectively as follows: 0.01≤x ≤ 0.1,0.01≤y≤0.1.
2. a kind of preparation method of blue long afterflow fluorescent powder, it is characterised in that the following steps are included:
(1) ingredient: with the CaCO of high-purity3、CaCl2、Al2O3、Eu2O3、Tm2O3、Gd2O3And La2O3As raw material, according to chemistry Form general formula Ca1-x-yAlO2Cl: xEu2+, yRe3+The proportion of middle each element accurately weighs each raw material；Wherein Re be Tm, Gd and The value range of one or more of La combination, x and y are respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1；
(2) mixing: above-mentioned raw materials are put into agate mortar, and to carry out ground and mixed uniform, is added when grinding according to total mass ratio 1:1 For dehydrated alcohol as abrasive media, milling time is 0.5 ~ 1 hour；
(3) it dries: the pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry under the conditions of 80 DEG C Sample and grinding distribution are taken out after the completion, obtain uniformly mixed raw material；
(4) be sintered: the uniformly mixed raw material is put into high temperature process furnances and is pre-sintered, sintering temperature be 1000 ~ 1300 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 7.5 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, It cools to room temperature after the completion of sintering with the furnace, obtains sintered body；
(5) select powder: the sintered body that step (4) are obtained carries out ball mill grinding, and using gas flow sizing machine to smashed powder It is classified according to particle size to get the blue long afterflow fluorescent powder.
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CN108753031A (en) 2018-11-06
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