CN108707357A - A kind of coating - Google Patents
A kind of coating Download PDFInfo
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- CN108707357A CN108707357A CN201810761037.4A CN201810761037A CN108707357A CN 108707357 A CN108707357 A CN 108707357A CN 201810761037 A CN201810761037 A CN 201810761037A CN 108707357 A CN108707357 A CN 108707357A
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- Prior art keywords
- acid
- doping
- phosphor
- coating
- ester
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Classifications
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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
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- 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
- 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
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
Abstract
The invention belongs to paint fields.A kind of coating, the coating include coating conventional ingredient and the phosphor powders, and phosphor powders are evenly distributed in coating conventional ingredient, and the addition of phosphor powders is 1 ~ 30%;The molecular formula of the phosphor is Yb/Eu/Er/Li:La2Hf2O7, for the doping that the doping for being 10 ~ 30%, Eu with the molar percent wherein doping of Yb is 1 ~ 10%, Er for 0.0001 ~ 0.01%, the doping of the Li is 10 ~ 30%;The phosphor can obtain the upper conversion green emission of Er3+ ions under 980nm shooting conditions, 298,365 under the excitation of 415nm xenon lamps, obtain the lower conversion red emission of Eu3+.The present invention can be applied to fitment material for family, family's electrical article, electronic product, image storage product etc., have wide range of applications as a kind of luminescent material.
Description
The application is divisional application, the applying date of original application:2017-11-21, original applying number:201711161441X,
The denomination of invention of original application:A kind of La2Hf2O7 systems phosphor and preparation method thereof.
Technical field
The invention belongs to paint fields.
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
It crosses 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 can obtain Er under the conditions of 980nm laser excitations3+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, it is not easy directly to answer
For optical anti-counterfeiting label material.
Invention content
It is an object of the present invention to provide a kind of La2Hf2O7System 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 to obtain having the feux rouges of different spectrum shapes to realize anti-fake.
In order to realize first above-mentioned purpose, present invention employs technical solutions below:
A kind of La2Hf2O7The molecular formula of system phosphor, the phosphor is Yb/Eu/Er: La2Hf2O7, 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 green emission of ion, 298,365
Under being excited with 415nm xenon lamps, Eu is obtained3+Lower conversion red emission.
Preferably, being mixing for 3 ~ 8%, Er with the doping that the molar percent wherein doping of Yb is 15 ~ 25%, Eu
Miscellaneous amount is 0.002 ~ 0.008%.As further preferably, with the doping that the molar percent wherein doping of Yb is 18 ~ 22%, Eu
Doping for 4 ~ 6%, Er is 0.004 ~ 0.006%.
In order to realize second above-mentioned purpose, present invention employs technical solutions below:
A kind of preparation method preparing the phosphor, this method include the following steps:
1)It will(10-25)% mMs of lanthanum 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 ethyl alcohol, stir 30-60 minutes
Obtain clear solution A;
2)It will(40-50)% mMs of acetylacetone,2,4-pentanedione hafnium is added in solution A, continues stirring 30-60 minutes;
3)By 2)In solution exist(40-60)DEG C heat preservation(1-2)Hour, until obtaining xerogel;
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.
Powder x-ray diffraction analysis shows:Obtained product is pure cubic phase La2Hf2O7.In 980nm laser irradiations
Under, Yb/Er/Eu: La2Hf2O7It can obtain Er3+Ion becomes clear yellow emission, and includes faint Eu in spectrum3+Shine wave
Section, under 298nm, 365nm and 415nm shooting condition, can obtain Eu3+Bright red emission.The present invention proposes to utilize
Yb/Eu/Er:La2Hf2O7System can obtain having different colours under different-waveband shooting condition and compose the luminous characteristics of shape
It realizes anti-fake.The characteristics of system, has:A, system can realize Eu under the excitation of the xenon lamp of different wave length3+Shine;B, system
It can realize that conversion shines up and down simultaneously, and emission peak derives from different rare earth ions, there is different luminescent colors and spectrum shape,
And a variety of rare earth ions are simply blended in some common matrix systems, due to larger radiationless between rare earth ion
Cross-relaxation probability, it is difficult to while realizing that conversion shines up and down, thus the system that the present invention utilizes can be applied to antifalsification label
Material.
The invention also discloses one kind La containing lithium2Hf2O7System phosphor, the molecular formula of the phosphor
For Yb/Eu/Er/Li: La2Hf2O7, the doping for being 10 ~ 30%, Eu with the molar percent wherein doping of Yb 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 is excited in 365nm, 395nm and 420nm xenon lamp
Under, obtain Eu3+Lower conversion red emission.
Preferably, being mixing for 3 ~ 8%, Er with the doping that the molar percent wherein doping of Yb is 15 ~ 25%, Eu
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
It is 18 ~ 22%.
It is a kind of to prepare the La2Hf2O7The preparation method of system phosphor, this method include the following steps:
1)It will(10-25)% mMs of lanthanum 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 ethyl alcohol
In, stirring obtains clear solution A in 30-60 minutes;
2)It will(40-50)% mMs of acetylacetone,2,4-pentanedione hafnium is added in solution A, continues stirring 30-60 minutes;
3)By 2)In solution exist(40-60)DEG C heat preservation(1-2)Hour, until obtaining xerogel;
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:La2Hf2O7 systems can be had under different-waveband shooting condition
There is the feux rouges of different spectrum shapes to realize anti-fake.Er can be obtained under 980nm shooting conditions3+The upper conversion green emission of ion,
298,365 under the excitation of 415nm xenon lamps, obtains Eu3+Lower conversion red emission.The characteristics of system, has:A, system can be
The xenon lamp excitation of different wave length is lower to realize Eu3+Red emission;B, system can realize that conversion shines up and down simultaneously, and emission peak comes
Derived from different rare earth ions, there is different luminescent colors;C, due to Li+It is glimmering that the introducing of ion substantially increases conversion
Luminous intensity utilizes the trace Er in ytterbium nitrate without adding erbium nitrate in raw material3+Can be realized it is luminous, and usually will be a variety of dilute
Native ion is co-doped in matrix, due to radiationless cross-relaxation probability larger between rare earth ion, it is difficult to while realizing high efficiency
Conversion up and down shine.The above feature shows 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 devices, using above-mentioned phosphor(The phosphor
Can be Yb/Eu/Er for above-mentioned structural formula:La2Hf2O7And Yb/Eu/Er/Li:La2Hf2O7One or both of mixing,
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
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 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 by suspension is prepared into phosphor powders particle suspension liquid solvent as described above, it is then coated with
In can be prepared in the substrate meet the present invention claims light-emitting component, but also contain polymer in the suspension
When matter, the sensitivity of final prepared light-emitting component and precision can be promoted 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, 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
It is 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, 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,
It is one or more in butanone, repefral and D-sorbite.
According to the present invention, the suspension of the phosphor powders particle is coated in the side on the substrate surface
Method can be the selection of this field routine can also use printing technique for example, the painting methods such as spraying, spin coating may be used.
Preferred printing technique prints the suspension of phosphor powders particle on the surface of the substrate to the present invention herein, so that
The sensitivity for the sensor being prepared and precision are further promoted.Wherein, the printing technique can be selected from dispensing,
One kind in inkjet printing, water transfer, silk-screen printing and roll-to-roll 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 obtaining the suspension blending and stirring or blending ultrasonic disperse.
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
Amount is 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 be added 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, by that will include that phosphor is formed in common paper, synthetic paper or epoxy resin, polyethylene, poly-
The macromolecules 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 combination 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 luminaires such as lamp, wind power lamp;Promptly, abnormal notification, very apparatus, dangerous display, very lamp, non-common mark, help work
Mark, signboard, the display device of tool;Safety guard hangs on nervous rope, animal protective fence around shop building;Ladder
Pedal, handrail and the mesh that is arranged in the state ofs being partly embedded in road etc. 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 roads the railway Deng Jie machine of flag
The exterior trim component for cutting road stick, bicycle, automobile, electric car, ship, aircraft etc. or build-in components, fishing tackle (simulation bait fishes
Pole, fishing net etc.;Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy (float, buoy);People, dog,
The position of the domestic animals such as the pets such as 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, holder, device, envelope, thickness
Paper, crust packaging, external 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 pieces 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;Operating device for operating audio devices and air-conditioning etc.;Family's electrical article, Portable
The input units such as device, electronic computer;Images storage means such as digital camera, CCD camera, film, photo, image etc..
New appearance is generated by so that phosphor is shone, therefore 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
The windmill of the ball etc. of the ball of baseball, table tennis ball, billiard ball (golf), luminous mechanism;Balloon;Laminated structure object 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
It carves, dynamic souvenir;Dynamic Display device;Luminous decorative device;The audio device such as loud speaker, the musical instrument (strings 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 quotient
Product;The water plant of the ornamental sink in aquarium etc., container;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., write organic ciphertext book at passport
Printed article or seal sealing element etc..
Using the photochemical catalyst activation for along with the luminous of phosphor, making to be attached to phosphor surface
Obtain, phosphor body-photochemical catalyst complex can be used for:The treatment of non-human animal, vehicle are helped in antibacterial, sterilization
The dirt purification of the antibacterial articles such as hand strap, handle, using the internal wall surface such as piping positioned at dark place fluid the energy of flow
The purification of amount.Inorganic luminous substance makes the photocrosslinking agent in macromolecule resin activate, can also promote to be crosslinked by shining.
By the way that the phosphor of the present invention with being mixed in resin, can be formed the resin combination of the present invention.
In addition, being formed again by the way that other inorganic material or organic material are further added 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 mixing machines 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 it relative to 100 parts by weight of Corvic, is compounded 50~200 mass parts of above-mentioned 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,
20~50 mass parts of above-mentioned phosphor are compounded, are carried out at 250~300 DEG C with double screw extruder, inflation processing machine
It is kneaded, molding, 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 it is band-like,
Plate, rodlike, partical phosphor body.In addition, by using injection (mo(u)lding) machine to partical at 170~200 DEG C
Phosphor body is processed molding, 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), gather alkenyl aroma hydroxy-aromatic resin
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,
The polyacrylic acid such as polyacrylonitrile, polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, gather at styrene-acrylonitrile copolymer (AS resins)
Copolymer, ethylene or the propylene of diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, liquid crystal polymer ethylene and propylene
With copolymer, ethylene 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 when object.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 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, ultra-violet absorber, light stabilizer, antistatic
Agent, fire retardant, fungicide, antiseptic, solidification catalyst, Photoepolymerizationinitiater initiater etc. are together with the phosphor of the present invention
Mixing, is shaped to rodlike, plate, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, flakey, piece
The arbitrary shapes such as shape, 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, glass flake, the 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.
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 purples 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 phenolic compound, phosphite ester based compound, phosphinate system chemical combination
Object and thioether based compound etc..
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- tertiary butyls -6- (3 '-tertiary butyls -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 oxides (4- methyl-6-tert-butylphenols), 2,2 '-di-2-ethylhexylphosphine oxides
(4- ethyl -6- tert-butyl phenols), 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-Methyls-benzyl-paracresol) 2,2 '-ethidines-bis- (4,6- di-t-butyls
Phenol), 2,2 '-butanes-bis- (4- methyl-6-tert-butylphenols), 4,4 '-butanes bis- (3 methy 6 tert butyl phenols),
Double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters of triethylene glycol-N-, the double [ of 1,6-HD;3- (bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) Bing Suanzhi ], Shuan [2- tertiary butyl -4- methyl 6- (3- tertiary butyl -5- methyl -2- hydroxybenzyls) Ben Ji ]It is right
Bis- { the 2-[ of phthalic acid ester, 3,9-;3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono Yang Ji ]- 1,1- dimethyl second
Base } four Yang Zaluo [ of -2,4,8,10-;5,5]Hendecane, 4,4 '-thiobis (6- tertiary butyls-metacresol), 4,4 '-thiobis (3-
Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), 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-
The double-[ of thiodiethylene;3- (3,5- di-tert-butyl-hydroxy phenyls) Bing Suanzhi ], bis- (just pungent sulfenyl) -6- (the 4- hydroxyls of 2,4-
Base -3 ', 5 '-di-tert-butyl amidos) -1,3,5- triazines, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy groups
Cinnamamide), N, the bis- [ of N '-;3- (3,5- di-tert-butyl-hydroxy phenyls) Bing Xianji ]The hydrazine, (2- methyl -4- 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-
(4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) isocyanuric acid ester, tri- 2[ of 1,3,5-;3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propiono Yang Ji ]Ethyl isocyanurate and Si [Methylene -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) Bing Suanzhi ]
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, bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, bis- (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyls) pentaerythrite diphosphorous acids
Ester, bis- { bis- (1- methyl-1s-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 is sub-
Phosphonate ester, four (2,4- di-tert-butyl-phenyls) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3,
3 '-biphenylens, four (2,6- di-tert-butyl-phenyls) -4,4 '-biphenylens, four (2,6- bis-
Tert-butyl-phenyl) -4,3 '-biphenylens, the sub- phosphine of four (2,6- di-tert-butyl-phenyls) -3,3 '-biphenylene two
Acid esters, bis- (2,4- di-tert-butyl-phenyls) -4- phenyl-phenyls phosphinates, bis- (2,4- di-tert-butyl-phenyls) -3- phenyl-benzene
Base phosphinate, bis- (2,6- di-n-butyls phenyl) -3- phenyl-phenyls phosphinates, bis- (2,6- di-tert-butyl-phenyls) -4- benzene
Base-phenylphosphite ester and bis- (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 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..
As benzophenone based compound, can enumerate:Benzophenone, 2,4 dihydroxyl benzophenone, 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- 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-
Tertiary butyl -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-
(5- tertiary butyl -2- hydroxy phenyls) benzotriazole, 2-[2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) Ben Ji ]Benzo three
Azoles, 2-[2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) Ben Ji ]- 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..
As oxanilide based compound, can enumerate:2- ethyoxyls -2 '-ethyloxanilide, 2- ethyoxyls -5-
Tertiary butyl -2 '-ethyloxanilide and 2- ethyoxyls -3 '-dodecyl butoxanilide etc..
As cyanoacrylate based compound, can enumerate:Ethyl -2- cyano -3,3 '-diphenylacrylate ester, 2-
Ethylhexyl-cyano -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 oxygroup) -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 oxygroup -2,2,6,6- tetramethyl piperidines, 4- benzyls oxygroup -2,2,
6,6- tetramethyl piperidines, 4- phenoxy group -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl oxygroup) -2,2,6,6- tetramethyls
Phenylpiperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl oxygroup) -2,2,6,
6- tetramethyl piperidines, bis- (2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) grass
Acid esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
Bis- (2,2,6,6- tetramethyl -4- piperidyls) adipate esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) terephthalates,
Bis- (2,2,6,6- tetramethyl -4- piperidyls the oxygroup)-ethane of 1,2-, α, the bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen of α ' -
Base)-paraxylene, bis- (2,2,6,6- tetramethyl -4- piperidyls)-toluylene -2,4- diurethanes, it is bis- (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 oxygroup } -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 '-tetramethyls -3,9-[Tetra- oxaspiros (5,5) of 2,4,8,10- 11
Wan ]The condensation product etc. of dimethanol.
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-bay
Amide propiono) quaternary ammonium salts system, sulfonate based compound, the 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 types 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..
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- 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
Oxygroup 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 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..
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-
Diamino -6- nonyl -1,3,5- triazines, 2,4- diamino -6- hydroxyl -1,3,5- triazines, dihydroxy -1,3 2- amino -4,6-,
5- triazines, 2,4- diamino -6- methoxyl group -1,3,5- triazines, 2,4- diamino -6- ethyoxyl -1,3,5- triazines, 2,4- diaminos
Base -6- propoxyl group -1,3,5- triazines, 2,4- diamino -6- isopropoxy -1,3,5- triazines, sulfydryl -1 2,4- diamino -6-,
3,5- triazines and 2- amino -4,6- dimercapto -1,3,5- triazines etc..
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, bis- bromo- 3- itrile groups propionyl of 2,2-
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
Close inorganic system's powder obtained from object.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 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 amide, aliphatic ketone, fatty acid part saponification ester, aliphatic acid low-carbon-ester, fat
Acid polyol ester, fatty acid polyglycol ethyl alcohol ester and modified organic silicon etc..
As aliphatic acid, can enumerate:Oleic acid, stearic acid, lauric acid, 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 be enumerated: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 numbers 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 18 or more the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline.
As the polyolefin of low molecular weight, can enumerate:Polyethylene wax, maleic acid modified polyethylene wax, the poly- second of oxidized form
5000 polyolefin below of alkene wax, haloflex wax and polypropylene wax equimolecular quantity.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 amides.
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- hydroxyethyls) stearmides.
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..
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 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
There are organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness of higher fatty acids to have
Machine silicon etc..
As solidification catalyst, can enumerate:(peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second
Ketone etc.) and organic peroxides, octyl 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 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..
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..
In turn, coating is mixed in which the inorganic hair of the present invention can also be made by matching the phosphor of the present invention
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 light emission luminance of the inorganic light-emitting coating composition of the present 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, antifoaming agent,
The coating such as antioxidant, the light stabilizer comprising ultra-violet absorber, fire retardant, solidification catalyst, fungicide and antiseptic
Use additive.
As the material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet light 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 ink film forming 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, EG single ethyl
Single ethylether of ether, the single-butyl ether of EG, 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, ethyl alcohol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol,
2- ethylhexyl alcohols), amide (C3~6, such as dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone), sulfoxide
(C2~4, such as dimethyl sulfoxide (DMSO)) and their mixed solvent of more than two kinds, water or aforementioned mixed solvent.As dispersion
Agent can enumerate as long as being macromolecule dispersing agent:Nai Huangsuanyan [Alkali metal (Na and K etc.) ] such as salt, ammonium salt;Formal
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 (the)s of C1~30 ]Phenol, aliphatic (C4~30) amine and aliphatic (C4~30) amide
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 (lauric acid, 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
[Alkyl (the)s of C1~30 ]Sulfonate alkali metal (same as described above) salt of 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 Yan [ of ester or bisphosphate;Alkali metal (same as described above) salt, quaternary ammonium salt etc. ].
(7) primary~tertiary amine salt form
The Zhi Fangzuan [ of C4~30;Primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and tertiary amine (dimethylstearamine
Equal)s ]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 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 according to purposes.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..
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 fat 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 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
At object, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and Gai Xingguiyou [Polyether modified silicon oil, (methyl) acrylate
Modified silicon oil modified silicon oil ]Deng.
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 bodies of polyisocyanate compound, buret bodies, 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 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:Melmac, 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
Fat and hexamethoxy methylated melamine, N, N, N ', N '-tetrakis hydroxymethyl phosphoniums 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, 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;Including the calcium silicates such as composite calcium silicate of calcium orthosilicate ingredient or calcium metasilicate ingredient;Calcium from
Son exchanges silica, magnesium ion exchanges the metal ion exchangeds silica such as silica;With preventing comprising Cr VI, lead etc.
Become rusty pigment etc..
As antifoaming agent, for example,:Silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness are poly-
The silicon-types such as siloxanes antifoaming agent, mineral oil system antifoaming agent, non-organic silicon polymer system antifoaming agent, comprising changing selected from organic
At least one kind of antifoaming agent in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol for including 18 or more carbon number
Antifoaming agent etc..
Light stabilizer, fire retardant, solidification catalyst, fungicide for antioxidant, comprising ultra-violet absorber and
Antiseptic etc. can enumerate aforementioned substances.
Description of the drawings
Yb/Er/Eu in Fig. 1, embodiment 1: La2Hf2O7X-ray diffractogram.
Yb/Er/Eu in Fig. 2, embodiment 1: La2Hf2O7Room temperature PL spectrum figure under the excitation of 980 nanometer lasers.
Yb/Er/Eu in Fig. 3, embodiment 1: La2Hf2O7Room temperature PL spectrum figure in the case where 298 nanometers of xenon lamps excite.
Yb/Er/Eu in Fig. 4, embodiment 1: La2Hf2O7Room temperature PL spectrum figure in the case where 365 nanometers of xenon lamps excite.
Yb/Er/Eu in Fig. 5, embodiment 1: La2Hf2O7Room temperature PL spectrum figure in the case where 415 nanometers of xenon lamps excite.
Yb/Er/Eu/Li in Fig. 6, embodiment 6: La2Hf2O7X-ray diffractogram.
Yb/Er/Eu/Li in Fig. 7, embodiment 6: La2Hf2O7Room temperature PL spectrum figure under the excitation of 980 nanometer lasers.
Yb/Er/Eu/Li in Fig. 8, embodiment 6: La2Hf2O7Room temperature PL spectrum figure in the case where 298 nanometers of xenon lamps excite.
Yb/Er/Eu/Li in Fig. 9, embodiment 6: La2Hf2O7Room temperature PL spectrum figure in the case where 365 nanometers of xenon lamps excite.
Yb/Er/Eu/Li in Figure 10, embodiment 6: La2Hf2O7Room temperature PL spectrum in the case where 415 nanometers of xenon lamps excite
Figure.
Specific implementation mode
Embodiment 6
By 1.52 mMs of lanthanum 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 ethyl alcohol, are stirred 30 minutes;Then 2 mMs of acetylacetone,2,4-pentanedione hafniums are added and stir 30 points
Clock;50o2 hours, which are kept the temperature, at a temperature of C obtains xerogel;Xerogel is ground 30 minutes, is then placed in Muffle furnace, in
700oC keeps the temperature 4 hours, and final product is obtained after furnace cooling.
Powder x-ray diffraction analysis shows:Products therefrom is pure cubic phase La2Hf2O7(Fig. 1).In 980nm laser irradiations
Under, Yb/Er/Eu: La2Hf2O7It can obtain Er3+Ion becomes clear green emission, and includes faint Eu in spectrum3+Shine wave
Section(Fig. 2).In 298nm(Fig. 3),365nm(Fig. 4)With 415nm(Fig. 5)Under xenon lamp shooting condition, Eu can be obtained3+Bright
Red emission.
Embodiment 2
By 1.68 mMs of lanthanum 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 ethyl alcohol, are stirred 30 minutes;Then 2 mMs of acetylacetone,2,4-pentanedione hafniums are added and stir 30
Minute;2 hours, which are kept the temperature, at a temperature of 50 DEG C obtains xerogel;Xerogel is ground 30 minutes, is then placed in Muffle furnace, in
700 DEG C keep the temperature 4 hours, and final product is obtained after furnace cooling.
Embodiment 3
By 1.42 mMs of lanthanum 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 ethyl alcohol, are stirred 30 minutes;Then 2 mMs of acetylacetone,2,4-pentanedione hafniums are added and stir 30
Minute;2 hours, which are kept the temperature, at a temperature of 50 DEG C obtains xerogel;Xerogel is ground 30 minutes, is then placed in Muffle furnace, in
700 DEG C keep the temperature 4 hours, and final product is obtained after furnace cooling.
Embodiment 4
50 grams of luminescent material for weighing embodiment 6, 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 green emission of ion, 298,365
Under being excited with 415nm xenon lamps, Eu is obtained3+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 green emission of ion, in 298,365 and 415nm xenons
Under lamp excitation, Eu is obtained3+Lower conversion red emission.The also antiforge function with magnetic characteristic.
Embodiment 6
By 1.52 mMs of lanthanum nitrates, 0.3 mM of ytterbium nitrate, 0.18 mM of europium nitrate, 0.002 mM of erbium nitrate, 0.2
MM lithium acetate and 2 mMs of citric acids are added in 8 milliliters of ethyl alcohol, are stirred 30 minutes;Then 2 mMs of acetyl are added
Acetone hafnium simultaneously stirs 30 minutes;50o2 hours, which are kept the temperature, at a temperature of C obtains xerogel;By xerogel grinding 30 minutes, then
It is placed in Muffle furnace, in 700oC keeps the temperature 4 hours, and final product is obtained after furnace cooling.
Powder x-ray diffraction analysis shows:Products therefrom is pure cubic phase La2Hf2O7(Fig. 1).In 980nm laser irradiations
Under, Yb/Er/Eu/Li: La2Hf2O7It can obtain Er3+Ion becomes clear green emission, and includes faint Eu in spectrum3+It shines
Wave band(Fig. 2).In 298nm(Fig. 3),365nm(Fig. 4)With 415nm(Fig. 5)Under xenon lamp shooting condition, Eu can be obtained3+It is bright
Red emission.
Embodiment 7
By 1.68 mMs of lanthanum 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 ethyl alcohol, are stirred 30 minutes;Then 2 mMs are added
Acetylacetone,2,4-pentanedione hafnium simultaneously stirs 30 minutes;2 hours, which are kept the temperature, at a temperature of 50 DEG C obtains xerogel;Xerogel is ground 30 minutes,
Then it is placed in Muffle furnace, keeps the temperature 4 hours in 700 DEG C, final product is obtained after furnace cooling.
Embodiment 8
By 1.42 mMs of lanthanum 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 ethyl alcohol, are stirred 30 minutes;Then 2 mMs are added
Acetylacetone,2,4-pentanedione hafnium simultaneously stirs 30 minutes;2 hours, which are kept the temperature, at a temperature of 50 DEG C obtains xerogel;Xerogel is ground 30 minutes,
Then it is placed in Muffle furnace, keeps the temperature 4 hours in 700 DEG C, final product is obtained after furnace cooling.
Embodiment 9
50 grams of luminescent material for weighing embodiment 6, 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 green emission of ion, 298,365
Under being excited with 415nm xenon lamps, Eu is obtained3+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 green emission of ion, in 298,365 and 415nm xenons
Under lamp excitation, Eu is obtained3+Lower conversion red emission.The also antiforge function with magnetic characteristic.
Claims (6)
1. a kind of coating, which is characterized in that the coating includes coating conventional ingredient and phosphor powders, inorganic light-emitting material
Feed powder end is evenly distributed in coating conventional ingredient, and the addition of phosphor powders is 1 ~ 30%;The inorganic light-emitting
The molecular formula of material is Yb/Eu/Er/Li: La2Hf2O7, it is 10 ~ 30%, Eu's with the molar percent wherein doping of Yb
The doping that doping is 1 ~ 10%, Er is 0.0001 ~ 0.01%, and the doping of the Li is 10 ~ 30%;The inorganic hair
Luminescent material can obtain the upper conversion green emission of Er3+ ions under 980nm shooting conditions, in 298,365 and 415nm xenon lamps
Under excitation, the lower conversion red emission of Eu3+ is obtained.
2. a kind of coating according to claim 1, which is characterized in that the phosphor, with molar percentage
It is the doping of 0.0002 ~ 0.008%, Li that the meter doping that wherein doping of Yb is 15 ~ 25%, Eu, which is the doping of 3 ~ 8%, Er,
Amount is 15 ~ 25%.
3. a kind of coating according to claim 1, which is characterized in that the phosphor, with molar percentage
It is the doping of 0.0004 ~ 0.006%, Li that the meter doping that wherein doping of Yb is 18 ~ 22%, Eu, which is the doping of 4 ~ 6%, Er,
Amount is 18 ~ 22%.
4. a kind of coating according to claim 1, which is characterized in that the addition of phosphor powders is 5 ~ 10%.
5. a kind of coating according to claim 1, which is characterized in that coating resin system can be polyamide, and chlorination is poly-
Propylene, polyurethane or acrylic acid.
6. a kind of coating according to claim 1, which is characterized in that coating is oil paint or water paint.
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CN201810761010.5A Withdrawn CN108961992A (en) | 2017-11-21 | 2017-11-21 | A kind of inorganic light-emitting device |
CN201810761039.3A Withdrawn CN108728096A (en) | 2017-11-21 | 2017-11-21 | A kind of suspension of phosphor powders particle |
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CN201810761017.7A Pending CN108728095A (en) | 2017-11-21 | 2017-11-21 | Phosphor is applied to optical anti-counterfeiting label material |
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CN201810761017.7A Pending CN108728095A (en) | 2017-11-21 | 2017-11-21 | Phosphor is applied to optical anti-counterfeiting label material |
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US20210253889A1 (en) * | 2020-02-18 | 2021-08-19 | Evonik Operations Gmbh | Composition for production of coatings having an antimicrobial property |
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CN108999033A (en) * | 2018-06-08 | 2018-12-14 | 滁州卷烟材料厂 | A kind of cigarette package fluorescence falsification preventing aluminium-foil paper |
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CN110223596B (en) * | 2019-07-09 | 2022-02-22 | 深圳大学 | Anti-counterfeit label based on stress luminescence |
CN111943669A (en) * | 2020-08-05 | 2020-11-17 | 西北工业大学 | Preparation method for synthesizing lanthanum hafnate powder by sol-gel method |
CN114479856B (en) * | 2021-11-09 | 2023-05-23 | 松山湖材料实验室 | Luminescent material, preparation method and application thereof |
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US4014812A (en) * | 1975-09-25 | 1977-03-29 | Gte Sylvania Incorporated | Method of preparing rare earth pyrohafnate phosphors |
CN101186768A (en) * | 2006-11-17 | 2008-05-28 | 姚瑞刚 | Integrated false-proof ink |
CN102265183A (en) * | 2008-12-30 | 2011-11-30 | 圣戈本陶瓷及塑料股份有限公司 | Scintillation device and method of producing a ceramic scintillator body |
DE102009000552B4 (en) * | 2009-02-02 | 2012-05-24 | Schott Ag | Active optoceramics with cubic crystal structure, their production and uses |
JP5517037B2 (en) * | 2009-08-06 | 2014-06-11 | 独立行政法人物質・材料研究機構 | Phosphor, method for manufacturing the same, and light emitting device using the same |
CN101665695B (en) * | 2009-09-25 | 2012-08-08 | 上海大学 | Preparation method of Pr3+ doped (Yx La (1-x)) 2O3 luminescent material |
CN103890982B (en) * | 2011-10-18 | 2016-08-24 | 株式会社村田制作所 | Light-emitting component, the manufacture method of light-emitting component and light-emitting device |
CN102515751A (en) * | 2011-12-20 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Upconversion luminescent transparent ceramic material and preparation method thereof |
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2017
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CN110184115A (en) * | 2019-07-04 | 2019-08-30 | 李洪 | Environmentally friendly coolant liquid and preparation method thereof |
US20210253889A1 (en) * | 2020-02-18 | 2021-08-19 | Evonik Operations Gmbh | Composition for production of coatings having an antimicrobial property |
US11713400B2 (en) * | 2020-02-18 | 2023-08-01 | Evonik Operations Gmbh | Composition for production of coatings having an antimicrobial property |
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