CN107903898B - A kind of Lu2Zr2O7System phosphor and preparation method thereof - Google Patents

Abstract

A kind of Lu₂Zr₂O₇System phosphor, the molecular formula of the phosphor are Yb/Eu/Er:Gd₂Ti₂O₇, the doping that the doping that the doping with molar percent wherein Yb is 10 ~ 30%, Eu is 1 ~ 10%, Er is 0.001 ~ 0.01%；The phosphor can obtain Er under 980nm shooting condition³⁺Red emission is converted on the approximate simple spectrum band of ion, at 361nm, 393nm, 414nm, the excitation of 465nm xenon lamp, obtains Eu³⁺Lower conversion red emission.System of the present invention can be realized simultaneously converts red emission up and down, and emission peak derives from different rare earth ions, with different spectrum shapes, and a variety of rare earth ions are simply blended in some common matrix systems, due to radiationless cross-relaxation probability biggish between rare earth ion, it is difficult to realize that conversion shines up and down simultaneously, thus the system that the present invention utilizes can be applied to antifalsification label material.

Description

A kind of Lu2Zr2O7System phosphor and preparation method thereof

Technical field

The invention belongs to phosphor fields.

Background technique

Optical anti-counterfeiting label is that special fluorescent material is designed to pattern or text, 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 level structure abundant, can be realized shining for different colours, such as by being co-doped with Yb/ Er can obtain Er under 980nm laser excitation condition³⁺Green emission, by being co-doped with Ce/Eu, under ultraviolet light irradiation, 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.

Summary of the invention

It is an object of the present invention to provide a kind of Lu₂Zr₂O₇System phosphor, second object of the present invention It is to provide the preparation method of above-mentioned phosphor, phosphor of the invention can be in different-waveband shooting condition Under 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 Lu₂Zr₂O₇The molecular formula of system phosphor, the phosphor is Yb/Eu/Er: Gd₂Ti₂O₇, the doping that the doping that the doping with molar percent wherein Yb is 10 ~ 30%, Eu is 1 ~ 10%, Er is 0.001~0.01%；The phosphor available Er under 980nm shooting condition³⁺The upper conversion yellow light of ion is sent out It penetrates, under the excitation of 365nm, 395nm and 420nm xenon lamp, obtains Eu³⁺Lower conversion red emission.

Preferably, being mixing for 3 ~ 8%, Er with the doping that the doping of molar percent wherein Yb is 15 ~ 25%, Eu Miscellaneous amount is 0.002 ~ 0.008%.As further preferably, doping that the doping with molar percent wherein 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) by (10-25) % mMs of lutecium nitrate, (2-9) % mMs of ytterbium nitrate, (0.5-4) % mMs of europium nitrate, (0.2-0.5) % mMs of erbium nitrate is added in (4-10) milliliter ethyl alcohol with (20-30) % mMs of citric acid, stirs 30-60 Minute obtains clear solution A；

2) (40-50) % mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；

3) by the solution in 2) in (40-60) DEG C heat preservation (1-2) hour, until obtaining xerogel；

4) 3) middle gained xerogel grinding (30-60) is placed in Muffle furnace after minute, and is burnt at (700-900) DEG C (4-8) hour is tied, obtains final product after furnace cooling.

The phosphor is applied to optical anti-counterfeiting label material.

The present invention material can obtain shining for different colours under the shooting condition of different wave length.Item is excited in 980nm Available Er under part³⁺The upper conversion yellow emission of ion obtains Eu under the excitation of 365nm, 395nm and 420nm xenon lamp³⁺'s Lower conversion red emission.The characteristics of system has: a, system can realize Eu under the excitation of the xenon lamp of different wave length³⁺Shine； B, system can realize that conversion shines up and down simultaneously, and emission peak derives from different rare earth ions, has different luminescent colors With spectrum shape, and a variety of rare earth ions are simply blended in some common matrix systems, due to larger between rare earth ion Radiationless cross-relaxation probability, it is difficult to while 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 Lu containing lithium₂Zr₂O₇System phosphor, the molecular formula of the phosphor For Yb/Eu/Er/Li:Lu₂Zr₂O₇, the doping that the doping with molar percent wherein Yb is 10 ~ 30%, Eu is 1 ~ The doping of 10%, Er are 0.0001 ~ 0.01%, and the doping of the Li is 10 ~ 30%；The phosphor exists Available Er under 980nm shooting condition³⁺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 doping of molar percent wherein 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 Lu₂Zr₂O₇The preparation method of system phosphor, this method include the following steps:

1) by (10-25) % mMs of lutecium nitrate, (2-9) % mMs of ytterbium nitrate, (0.5-4) % mMs of europium nitrate, (0- 0.5) % mMs of erbium nitrate, (5-10) % mMs of lithium acetate and (20-30) % mMs of citric acid are added to (4-10) milliliter In ethyl alcohol, stirring obtains clear solution A in 30-60 minutes；

2) (40-50) % mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；

3) by the solution in 2) in (40-60) DEG C heat preservation (1-2) hour, until obtaining xerogel；

4) 3) middle gained xerogel grinding (30-60) is placed in Muffle furnace after minute, and is burnt at (700-900) DEG C (4-8) hour is tied, obtains final product after furnace cooling.

The phosphor is applied to optical anti-counterfeiting label material.

The present invention proposes to utilize Yb/Eu/Er/Li:Lu₂Zr₂O₇System can be had under different-waveband shooting condition There is the feux rouges of different spectrum shapes to realize anti-fake.The material can obtain shining for different colours under the shooting condition of different wave length.? Available Er under 980nm shooting condition³⁺The upper conversion yellow emission of ion is excited in 365nm, 395nm and 420nm xenon lamp Under, obtain Eu³⁺Lower conversion red emission.The characteristics of system has: a, system can be real under the excitation of the xenon lamp of different wave length Existing Eu³⁺Shine；B, system can realize that conversion shines up and down simultaneously, and emission peak derives from different rare earth ions, has not Same luminescent color;C, due to Li⁺The introducing of ion substantially increases up-conversion fluorescence intensity, is not necessarily to add nitre in raw material Sour erbium utilizes the trace Er in ytterbium nitrate³⁺It can be realized luminous, and usually a variety of rare earth ions be co-doped in matrix, due to dilute Biggish radiationless cross-relaxation probability between native ion, it is difficult to while realizing that efficient conversion up and down shines.The above feature The system for showing 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 (phosphor It can be Yb/Eu/Er/Li:Lu for above-mentioned structural formula₂Zr₂O₇And Yb/Eu/Er:Lu₂Zr₂One or both of O mixing, Phosphor described below be one or both of two kinds of structural formulas mixing) made of substrate.

The invention also discloses a kind of inorganic light-emitting device, including substrate and the inorganic luminescence thin film being 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 being attached in substrate, The inorganic luminescence thin film is phosphor powders or phosphor thin slice.

Preferably, inorganic luminescence thin 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 inorganic light-emitting device preparation method, comprising: by the outstanding of phosphor powders particle as described above Supernatant liquid is coated in substrate as described above.

Although being then coated with suspension is prepared into phosphor powders particle suspension liquid solvent as described above 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 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 phosphor powders particle is coated in the side on the substrate surface Method can be the selection of this field routine, for example, can also use printing technique using coating methods such as spraying, spin coatings. 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 selected from dispensing, One of 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- terephthaldehyde 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 additional amount 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 is also possible to 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 additional amount 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 is also possible to water paint.

In addition, by that will be formed in common paper, synthetic paper or epoxy resin comprising phosphor, polyethylene, gather 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 their combination and their fabricated product etc. Exterior trim surface, or by containing phosphor in inside.

Inorganic light-emitting device of the present invention can be used as illumination, for safety display utilization.Such as are as follows: device vibration 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 road 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, bracket, device, envelope, thickness Paper, crust packaging, external overlay film), (manually shine medical products (breathing assistance utensil, experimental study equipment) hair for robot Structural body, artificial shiny skin, manually shine body) etc..As coating composition, ink composition, cement, surface dopant In the utilization example containing phosphor, can enumerate: financial institution, community organization, credit card company, in circulation industry etc. The mail pieces such as the crimping postcard sheet material in bonding agent use, stickup containing phosphor；The families such as chair, bed Tool；The building materials such as flooring material, ceramic tile, wall material, prefabricated board material, paveio(u)r, timber steel concrete；It is equipped on The automated navigation system device of vehicle；For operating the operating device of audio devices and air-conditioning etc.；Family electrical article, Portable The input units such as device, electronic computer；Images storage means such as digital camera, CCD camera, film, photo, image etc..

It can produce new appearance and making phosphor shine, therefore also consider to toy, lipuid goods etc. Entertain the expansion of commodity, daily necessity.For example: wind long narrow flag, swing, the fast ski-running 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 (golf, the ball of baseball, table tennis ball, ball of billiard ball etc.), luminous mechanism；Balloon；Laminated structure object is paper , batch flute, paper folding, paper balloon, folding fan, New Year card, draw 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 loudspeaker, 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 shining along with phosphor, make to be attached to the photochemical catalyst activation on phosphor surface and 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 utilizes the energy of flow of the fluid of wall surface inside piping for being located at dark place etc. The purification of amount.Inorganic luminous substance activates the photocrosslinking agent in macromolecule resin, can also promote to be crosslinked by shining.

By the way that phosphor of the invention with being mixed in resin, can be formed resin combination of the invention.

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 phosphor body 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 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 where 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 above-mentioned 50~200 mass parts of phosphor, calcium-zinc system and stablizes 3~5 mass parts of agent, 30~100 mass parts of dioctyl phthalate as plasticizer, with two-roller mill at 150~200 DEG C It is kneaded, so as to obtain the phosphor body with flexible sheet.

When obtaining the phosphor body of film-form, such as relative to 100 mass parts of pet resin, Above-mentioned 20~50 mass parts of phosphor are compounded, are carried out 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 formed, 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 carries out machine-shaping, the phosphor body 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. are together with phosphor of the 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, 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 inorganic hair of the invention can also be made with coating is mixed in phosphor of the invention Photosensitiveness coating composition.

Inorganic light-emitting coating composition of the 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 invention containing phosphor of the invention Height, therefore visual high coating can be carried out.

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

The X-ray diffractogram of Yb/Er/Eu:Lu2Zr2O7 in Fig. 1, embodiment 1.

Room temperature PL spectrum figure of the Yb/Er/Eu:Lu2Zr2O7 under the excitation of 980 nanometer lasers in Fig. 2, embodiment 1.

Room temperature PL spectrum figure of the Yb/Er/Eu:Lu2Zr2O7 in the case where 365 nanometers of xenon lamps excite in Fig. 3, embodiment 1.

Room temperature PL spectrum figure of the Yb/Er/Eu:Lu2Zr2O7 in the case where 395 nanometers of xenon lamps excite in Fig. 4, embodiment 1.

Room temperature PL spectrum figure of the Yb/Er/Eu:Lu2Zr2O7 in the case where 420 nanometers of xenon lamps excite in Fig. 5, embodiment 1.

The X-ray diffractogram of Yb/Er/Eu/Li:Lu2Zr2O7 in Fig. 6, embodiment 6.

Room temperature PL spectrum of the Yb/Er/Eu/Li:Lu2Zr2O7 under the excitation of 980 nanometer lasers in Fig. 7, embodiment 6 Figure.

Room temperature PL spectrum of the Yb/Er/Eu/Li:Lu2Zr2O7 in the case where 365 nanometers of xenon lamps excite in Fig. 8, embodiment 6 Figure.

Room temperature PL spectrum of the Yb/Er/Eu/Li:Lu2Zr2O7 in the case where 395 nanometers of xenon lamps excite in Fig. 9, embodiment 6 Figure.

Room temperature PL spectrum of the Yb/Er/Eu/Li:Lu2Zr2O7 in the case where 420 nanometers of xenon lamps excite in Figure 10, embodiment 6 Figure.

Specific embodiment

Embodiment 1

By 1.52 mMs of lutecium nitrates, 0.3 mM of ytterbium nitrate, 0.18 mM of europium nitrate, 0.002 mM of erbium nitrate And 2 mMs of citric acids are added in 8 milliliters of ethyl alcohol, are stirred 30 minutes；Then 2 mMs of basic zirconium chlorides are added and stir 30 Minute；50^o2 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 700^oC 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 Lu₂Zr₂O₇(Fig. 1).In 980nm laser irradiation Under, Yb/Er/Eu:Lu₂Zr₂O₇Available Er³⁺Ion becomes clear yellow emission, and includes faint Eu in spectrum³⁺Shine wave Section (Fig. 2).In 365nm(Fig. 3), 395nm(Fig. 4) with 420nm(Fig. 5) under xenon lamp shooting condition, available Eu³⁺Bright Red emission.

Embodiment 2

By 1.68 mMs of lutecium nitrates, 0.2 mM of ytterbium nitrate, 0.12 mM of europium nitrate, 0.005 mM of nitric acid Erbium and 2 mMs of citric acids are added in 8 milliliters of ethyl alcohol, are stirred 30 minutes；Then 2 mMs of basic zirconium chlorides are added and stir 30 minutes；Xerogel is obtained within 2 hours in 50 DEG C of at a temperature of heat preservation；Xerogel is ground 30 minutes, is then placed in Muffle furnace, 4 hours are kept the temperature in 700 DEG C, final product is obtained after furnace cooling.

Embodiment 3

By 1.42 mMs of lutecium nitrates, 0.5 mM of ytterbium nitrate, 0.08 mM of europium nitrate, 0.001 mM of nitric acid Erbium and 2 mMs of citric acids are added in 8 milliliters of ethyl alcohol, are stirred 30 minutes；Then 2 mMs of basic zirconium chlorides are added and stir 30 minutes；Xerogel is obtained within 2 hours in 50 DEG C of at a temperature of heat preservation；Xerogel is ground 30 minutes, is then placed in Muffle furnace, 4 hours are kept the temperature in 700 DEG C, final product is obtained after furnace cooling.

Embodiment 4

50 grams of luminescent material of embodiment 1 are weighed, with 150 grams of ink vehicles (80 grams of phenolic resin oil, alkyd resin oil 40 grams, 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.The available Er under 980nm shooting condition³⁺The upper conversion yellow emission of ion, in 365nm, Under 395nm and the excitation of 420nm xenon lamp, 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 make At printing ink, except the available Er under 980nm shooting condition³⁺The upper conversion yellow emission of ion, in 365nm, 395nm with Under the excitation of 420nm xenon lamp, Eu is obtained³⁺Lower conversion red emission.Also with the antiforge function of magnetic characteristic.

Embodiment 6

By 1.52 mMs of lutecium nitrates, 0.3 mM of ytterbium nitrate, 0.18 mM of europium nitrate, 0.002 mM of nitric acid Erbium, 0.2 mM of lithium acetate and 2 mMs of citric acids are added in 8 milliliters of ethyl alcohol, are stirred 30 minutes；Then 2 millis are added Mole basic zirconium chloride simultaneously stirs 30 minutes；50^o2 hours, which are kept the temperature, at a temperature of C obtains xerogel；Xerogel is ground 30 points Then clock is placed in Muffle furnace, in 700^oC 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 Lu₂Zr₂O₇(Fig. 6).In 980nm laser irradiation Under, Yb/Er/Eu/Li:Lu₂Zr₂O₇Available Er³⁺Ion becomes clear yellow emission, and includes faint Eu in spectrum³⁺It shines Wave band (Fig. 7).In 365nm(Fig. 8), 395nm(Fig. 9) with 420nm(Figure 10) under xenon lamp shooting condition, available Eu³⁺It is bright Bright red emission.

Embodiment 7

By 1.68 mMs of lutecium nitrates, 0.2 mM of ytterbium nitrate, 0.12 mM of europium nitrate, 0.001 mM of nitric acid Erbium, 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 mmoles are added That basic zirconium chloride simultaneously stirs 30 minutes；Xerogel is obtained within 2 hours in 50 DEG C of at a temperature of heat preservation；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 lutecium nitrates, 0.5 mM of ytterbium nitrate, 0.08 mM of europium nitrate, 0.001 mM of nitric acid Erbium, 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 mmoles are added That basic zirconium chloride simultaneously stirs 30 minutes；Xerogel is obtained within 2 hours in 50 DEG C of at a temperature of heat preservation；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 of embodiment 6 are weighed, with 150 grams of ink vehicles (80 grams of phenolic resin oil, alkyd resin oil 40 grams, 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.The available Er under 980nm shooting condition³⁺The upper conversion yellow emission of ion, in 365nm, Under 395nm and the excitation of 420nm xenon lamp, 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 make At printing ink, except the available Er under 980nm shooting condition³⁺The upper conversion yellow emission of ion, in 365nm, 395nm with Under the excitation of 420nm xenon lamp, Eu is obtained³⁺Lower conversion red emission.

Claims (4)

1. a kind of Lu₂Zr₂O₇System phosphor, which is characterized in that the Lu₂Zr₂O₇The molecule of system phosphor Formula is Yb/Eu/Er:Lu₂Zr₂O₇, the doping that the doping with molar percent wherein Yb is 10 ~ 30%, Eu for 1 ~ 10%, The doping of Er is 0.001 ~ 0.01%；The Lu₂Zr₂O₇System phosphor can obtain under 980nm shooting condition To Er³⁺The upper conversion yellow emission of ion obtains Eu under the excitation of 365nm, 395nm and 420nm xenon lamp³⁺Lower conversion feux rouges Transmitting.

2. a kind of Lu according to claim 1₂Zr₂O₇System phosphor, which is characterized in that with molar percentage The doping that the doping that the doping for counting wherein Yb is 15 ~ 25%, Eu is 3 ~ 8%, Er is 0.002 ~ 0.008%.

3. a kind of Lu according to claim 1₂Zr₂O₇System phosphor, which is characterized in that with molar percentage The doping that the doping that the doping for counting wherein Yb is 18 ~ 22%, Eu is 4 ~ 6%, Er is 0.004 ~ 0.006%.

4. a kind of prepare Lu described in any one claim 1 ~ 3₂Zr₂O₇The preparation method of system phosphor, it is special Sign is that this method includes the following steps:

1) by (10-25) % mMs of lutecium nitrate, (2-9) % mMs of ytterbium nitrate, (0.5-4) % mMs of europium nitrate, (0.2- 0.5) % mMs of erbium nitrate is added in (4-10) milliliter ethyl alcohol with (20-30) % mMs of citric acid, is stirred 30-60 minutes Obtain clear solution A；

2) (40-50) % mMs of basic zirconium chloride is added in solution A, continues stirring 30-60 minutes；

3) by the solution in 2) in (40-60) DEG C heat preservation (1-2) hour, until obtaining xerogel；

4) 3) middle gained xerogel grinding (30-60) is placed in Muffle furnace after minute, and in (700-900) DEG C sintering (4- 8) hour obtains final product after furnace cooling.