CN107936963B - A kind of green tribo-luminescence fluorescent powder and preparation method thereof - Google Patents

A kind of green tribo-luminescence fluorescent powder and preparation method thereof Download PDF

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CN107936963B
CN107936963B CN201711061638.6A CN201711061638A CN107936963B CN 107936963 B CN107936963 B CN 107936963B CN 201711061638 A CN201711061638 A CN 201711061638A CN 107936963 B CN107936963 B CN 107936963B
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tribo
acid
luminescence
green
fluorescent powder
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CN107936963A (en
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杨道救
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Guizhou Saiyi Photoelectric Technology Co.,Ltd.
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杨陈燕
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Priority to CN201811107660.4A priority Critical patent/CN108949170A/en
Priority to CN201811107246.3A priority patent/CN109054818A/en
Priority to CN201811107765.XA priority patent/CN109054819A/en
Priority to CN201711061638.6A priority patent/CN107936963B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media

Abstract

The invention discloses a kind of green tribo-luminescence fluorescent powders and preparation method thereof, it is desirable to provide a kind of pressure sensitive material with tribo-luminescent performance belongs to phosphor technologies field.The chemical composition general formula of the fluorescent powder is Sr3‑x‑yAl2SiO8:xEu2+,yGa3+, the value range of x and y is respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1, and the centre of luminescence of the fluorescent powder is Eu2+Ion, by introducing Ga3+Ion can effectively enhance its tribo-luminescence effect.Fluorescent powder provided by the invention has apparent tribo-luminescence effect, the pressure sensitive component that can be used in pressure sensor.

Description

A kind of green tribo-luminescence fluorescent powder and preparation method thereof
Technical field
The invention belongs to luminescent material technical fields, more particularly to a kind of green tribo-luminescence fluorescent powder and its preparation side Method.
Background technique
The phenomenon for causing its luminous in solid by action of mechanical pressure is tribo-luminescence, in broad terms, alternatively referred to as Machinery shines.Shining for tribo-luminescence and other forms, such as thermoluminescence and chemiluminescence, is often not easy to distinguish.For example it is rubbing It wipes in luminescence experiments, the mechanical energy acted on crystal can be converted into thermal energy, and then cause thermoluminescence；Or have occurred one The chemical reaction of excitation state product is generated so as to cause shining.These effects are referred to alternatively as tribothermoluminescence, tribochemistry respectively It shines.It is also included in triboluminescent definition when two hardware tap mutually (or thermal friction) and incandescent glisten with two kinds not occurs With two kinds of light emitting species for generating electric arc when object friction by electrostatic.Such as early in the mercury of the report of Picard in 1675 in glass surface Luminescence phenomenon caused by flowing just belongs to this.For exciting triboluminescent mechanical energy, there are many forms, such as temperature vibration, it can To generate stress, crackle and crystal-phase transformation；Crystallization rapidly, it also can produce stress and crack；There are also by the crystal that collides, rubs And the anisotropic pressure and fluid generated is in surface of solids movement etc..Triboluminescent history is longer, is in 17 generation earliest Discipline is reported by Francis Bacon, has recorded the friction observed earliest in his written " progress in study " text Luminescent crystal, and say friction sugar when can release light.
Manufactured luminescent material is wrapped up using tribo-luminescence substance, can be used to manufacture pressure detecting sensors, be examined with light It surveys element to be used in combination, the display element in energy development of new pressure detecting sensors, forecast monitor and certain scientific instrument Deng.And this novel sensing mode that friction pressure is converted to luminosity, friction pressure is converted to compared to old-fashioned Amount of electrons has contactless inductive and is electrically connected simpler advantage if strain sensing and piezoelectric type sense, thus can be more Widely it is applied.In recent years, some that there is unique photoluminescent property, have been used for the chemical combination for manufacturing all kinds of fluorescent materials Object is found to have tribo-luminescent performance again, they are increasingly valued by people.But it is not all that there is good fluorescence The material of characteristic all has excellent tribo-luminescence property, only certain containing specific ligand and with specific crystal knot The fluorescent material of structure just has tribo-luminescence characteristic.Some attempt to excite air to solve from the angle of crystal structure and friction It releases and discloses tribo-luminescence mechanism, but scientific circles there is no final conclusion to this so far.Since triboluminescent mechanism is still unclear so far Chu, so on the one hand people are dedicated to the developmental research of practical application, on the other hand make great efforts to explore triboluminescent mechanism and its Dynamic process.
Summary of the invention
Tribo-luminescence substance is paid close attention in materials science field by people.Tribo-luminescence is due to Solid Mechanics energy application Light emitting, be associated with the spectral composition of solid, mechanics and electrical properties.Tribo-luminescence is studied actually with which because being known as It closes, how to select most suitable experiment condition, targetedly synthesize tribo-luminescence body, with important theory and practical meaning Justice.
The disadvantages of in order to overcome the luminous intensity of above-mentioned triboluminescent material in the prior art weaker, the present invention provides one Kind has the phosphor material powder and preparation method thereof of higher tribo-luminescence efficiency, which has apparent green tribo-luminescence Effect, the pressure sensitive component that can be used in pressure sensor.
To solve above-mentioned the deficiencies in the prior art, the technical solution adopted in the present invention is as follows:
A kind of green tribo-luminescence fluorescent powder, the chemical composition general formula of the fluorescent powder are Sr3-x-yAl2SiO8: xEu2+,yGa3+, the value range of x and y is respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1.Particularly, the fluorescent powder shine in The heart is Eu2+Ion, by introducing Ga3+Ion is distorted lattice, generates defect level, can effectively enhance its friction hair Light effect.
A kind of preparation method of green tribo-luminescence fluorescent powder, it is characterised in that the following steps are included:
(1) ingredient: with the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr3-x-yAl2SiO8: xEu2+, yGa3+The proportion of middle each element accurately weighs each raw material；
(2) mixing: above-mentioned raw materials are put into agate mortar, and to carry out ground and mixed uniform, according to total mass ratio 1:1 when grinding Dehydrated alcohol is added as abrasive media, milling time is 0.5 ~ 1 hour；
(3) it dries: the pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours under the conditions of 80 DEG C, Sample and grinding distribution are taken out after the completion of dry, obtain uniformly mixed raw material；
(4) be sintered: the uniformly mixed raw material is put into high temperature process furnances and is sintered, sintering temperature be 1100 ~ 1400 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, It cools to room temperature after the completion of sintering with the furnace, obtains sintered body；
(5) it selects powder: the sintered body that step (4) obtain being ground in the agate mortar and is rubbed to get a kind of green Wipe luminescent phosphor.
Compared with prior art, the beneficial effects of the present invention are:
(1) the present invention provides a kind of green tribo-luminescence fluorescent powder, matrix group becomes Sr3Al2SiO8, pass through rare earth Ion Eu2+Doping obtains green tribo-luminescence, and luminous peak position is identified in 535nm convenient for human eye；
(2) by introducing Ga3+Ion is distorted lattice, generates defect level, can effectively enhance its tribo-luminescence Effect；
(3) preparation process of green tribo-luminescence fluorescent powder provided by the invention is simple, is convenient for industrialized production.
The invention also discloses a kind of stress irradiance elements, using base made of above-mentioned green tribo-luminescence fluorescent powder Piece.
The invention also discloses a kind of stress irradiance element, including substrate and the pressure light-emitting film being attached in substrate, The pressure light-emitting film is above-mentioned green tribo-luminescence phosphor powder or green tribo-luminescence fluorescent powder thin slice.
The invention also discloses the pressure light-emitting film that a kind of stress irradiance element includes substrate and is attached in substrate, institutes The pressure light-emitting film stated is green tribo-luminescence phosphor powder or green tribo-luminescence fluorescent powder thin slice.
Preferably, pressure light-emitting 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 stress irradiance part making method, comprising: will green tribo-luminescence phosphor powder as described above The suspension of grain is coated in substrate as described above.
Although by suspension is prepared into green tribo-luminescence phosphor powder particle suspension liquid solvent as described above, so Be coated in the substrate afterwards can prepare meet the present invention claims sensor, but also contain high score in the suspension When sub- substance, the sensitivity of final prepared sensor and precision can be promoted further.
The content of the green tribo-luminescence phosphor powder particle can also change in a wider scope, preferable case Under, the content of the suspension based on 100 parts by weight, the green tribo-luminescence phosphor powder particle is 0.5-10 weight Part, preferably 1-5 parts by weight.
Preferably, the polymer substance is selected from PVA, EVA (ethene-vinyl acetate copolymer), PDMS, PU, PMMA (gather Methyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), starch, cellulose, natural plant gum, animal One of glue, carboxymethyl starch, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose are a variety of.
According to the present invention, the content of the polymer substance can also change in a wider scope, under preferable case, base In the suspension of 100 parts by weight, the high molecular content is 1-10 parts by weight, preferably 3-8 parts by weight.
According to the present invention, the solvent can be various solvents commonly used in the art, be preferably selected from water, methanol, second Alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol phenyl ether, second two Alcohol benzyl oxide, health alcohol, diethylene glycol methyl ether, diethylene glycol ether, butyl carbitol, triethylene glycol methyl ether, diacetone alcohol, tridecanol, 14 Alcohol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, dimethylbenzene, bicyclohexyl, hexamethylene, n-butanol, One of butanone, repefral and D-sorbite are a variety of.
According to the present invention, the suspension of the green tribo-luminescence phosphor powder particle is coated in the substrate surface On method can be the selection of this field routine, for example, can also use and beat using the coating methods such as spraying, spin coating Print technology.The suspension of green tribo-luminescence phosphor powder particle is imprinted on the table of substrate to the present invention by preferred printing technique herein On face, so that the sensitivity for the sensor being prepared and precision are further promoted.Wherein, the printing technique It can be selected from one of dispensing, inkjet printing, water transfer, silk-screen printing and roll-to-roll printing.When using printing technique by institute When stating the suspension print of green tribo-luminescence phosphor powder particle on the surface of the substrate, preferably the suspension is prepared into Ink, the preparation method of the ink are by obtaining the suspension blending and stirring or blending ultrasonic disperse.
Green tribo-luminescence phosphor powder particle, pressure sensitive component as described above and institute as above of the present invention Application of the pressure sensor for the method preparation stated in wind tunnel experiment.
The invention also discloses a kind of stress irradiance element, which includes high molecular material and described green Color tribo-luminescence phosphor powder, green tribo-luminescence phosphor powder are evenly distributed in high molecular material, green friction hair The additional amount of emitting phosphor powder is 1 ~ 90%；Preferably 10 ~ 80%.High molecular material can be selected from PDMS (polydimethylsiloxanes Alkane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimides) and PVA (poly- second Enol) 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 green tribo-luminescence fluorescence Powder powder, green tribo-luminescence phosphor powder are evenly distributed in ink conventional ingredient, green tribo-luminescence phosphor powder Additional amount be 1 ~ 30%；Preferably 5 ~ 10%.Ink resin system can be polyamide, chlorination polypropylene, polyurethane or propylene Acid.Either oil-based ink is also possible to water-based ink.
The invention also discloses a kind of coating, which includes coating conventional ingredient and the green tribo-luminescence fluorescence Powder powder, green tribo-luminescence phosphor powder are evenly distributed in coating conventional ingredient, green tribo-luminescence phosphor powder Additional amount be 1 ~ 30%；Preferably 5 ~ 10%.Coating resin system can be polyamide, chlorination polypropylene, polyurethane or propylene Acid.Either oil paint is also possible to water paint.
In addition, by that will be formed in common paper, synthetic paper or epoxy resin comprising green tribo-luminescence fluorescent powder, gather The macromolecules such as ethylene, polyethylene terephthalate, polyester, polypropylene, polyvinyl chloride raw material, natural rubber or synthesis rubber Glue, glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete or their combination and their fabricated product Deng exterior trim surface, or by inside containing green tribo-luminescence fluorescent powder, so as to detect exception, or by applying punching It hits wave and diagnoses the deterioration (stress-strain detection, stress distribution measurement) of various works, component.Such as are as follows: mansion building The large structures such as object, overpass, bridge, road, rail, pillar, tower, pipeline and tunnel, flooring material, ceramic tile, wall material The driving members such as construction materials, gear, the cam such as material, prefabricated board material, paveio(u)r, timber, steel, concrete, bicycle, Exterior trim component or build-in components used in automobile, electric car, ship, aircraft etc. (engine components, tire, belt etc.), bearing Connections component such as component, bearing retainer and bearing, screw, screw rod, nut, washer with optical sensor etc..Separately Outside, as its application, can expect: detection battery, water supplying pipe, sprinkler head, is filled with electrolyte or polymer electrolytic at valve seat The leakage of the nonaqueous electrolytic solution secondary battery of matter.Furthermore it is possible to make the bonding of the bonding agent containing green tribo-luminescence fluorescent powder The distribution visualization of oxidant layer internal stress, can also hold the cracking of bonding agent.
When using green tribo-luminescence fluorescent powder as stress irradiance element, it can be used for pressure-sensitive device, touch screen, touch-control and pass Sensor, photodiode or phototransistor, piezoelectric actuator or electrostatic actuators, photism polymer actuator, liquid measure inspection It surveys device, impact force detector part, optical waveguide, optical waveguide device, mechanical optics device, detection device, information processing unit, open The e-machines such as pass, operation button, input unit, finger-impu system and machine can carry out the non-contact of device and system Control, automation process, remote control operation.For example: the elevation measurement device of the connection terminal of semiconductor component, hole The measurement device of phenomenon occurrence quantity, the measurement device of sound pressure distribution, using medical examination ultrasonic wave sound pressure Distribution and energy density distribution measurement device, the stress that the components such as the graft for being installed on organism bone or analog bone are acted on The measurement device of the distribution of strain, the dress for transmitting hawser, transmission device and laser processing device, the amount of bow for detecting steering shaft It sets, the radiation camera of the position of specific photographed region, the depth of parallelism check device of flow rate detector mould pressurizing machine, energy Enough generate stress corresponding with the thermal energy of infrared light and image solid-state imaging apparatus, by frictional force, shearing force, impact The mechanical external forces such as power, pressure be converted into optical signal and transmit light head, using the light head by remote control operation machinery device Remote-control switching system and using light head detection couple detection system, be removably installed in it is electrical, electronics, machinery The dismounting body of the main part of various machines, such as ink-jet printer print cartridge, be able to detect with the installation condition of paper carton and not The detection device and dismounting body of the dismounting body of installation condition；It can check that the ultraviolet light for remaining on bump is solid in a short time The imprinting apparatus for changing resin, the operating device for not needing wiring, can be directed into organism, dark place it is small-sized and radio-type Light source (stress irradiance particle), the check device for having it and inspection method, stress placement file system etc..In addition, can also To be used for: gasket, the measurement of the leakproofness of sealing element, the ground plane shape of tire, the measurement of earth contact pressure distribution, gear division bite force Measurement, the grounding parts tools for measurement of tire, the measuring method of cavitation occurrence quantity etc..
It can also be used as tactile sensor element application.For example: people coordinates humanoid robot, artificial hand vacation refers to Artificial limb, the distinctor of diagnosis, hardness pliability detector of various industry etc..In addition, by measurement due to radiation The luminous energy of effect and generation, to can also expect the meter of metering and the exposure intensity distribution of the radiant exposure of radiation Amount.
Other than said determination device, it is also contemplated that as illumination, for safety display utilization.Such as Are as follows: device vibrates the luminaires such as lamp, wind power lamp；Promptly, abnormal notification, very apparatus, dangerous display, very lamp, non-common Mark, the mark of help tool, signboard, display device；Safety guard hangs on nervous rope around shop building, animal Protective fence；Use filament to the pedal of ladder, handrail and the mesh that is arranged in the state ofs being partly embedded in road etc.；Health promoting appliance, Walking assisting device tool (walking auxiliary walking stick, the notification that shines antenna etc.)；The jewellery such as earrings, necklace；Support pillar, the railway of flag The exterior trim component or build-in components, fishing tackle of the road the Deng Jie road Ji Jie stick, bicycle, automobile, electric car, ship, aircraft etc. (simulation bait, fishing rod, fishing net etc.；Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy it is (float, floating Mark)；The position of the domestic animals such as the pets such as people, dog, cat, ox, pig, sheep, chicken etc. is shown；Fan (the blade of wind-power electricity generation, ventilating fan etc. Deng), clothes (shoes, gym suit, manually shine cloth, artificial luminous filament, artificial luminescent fibre etc.)；Packaging (case, bracket, device, Envelope, ground paper, crust packaging, external overlay film), medical products (breathing assistance utensil, experimental study equipment) robot (artificial hair Light hair structure body, artificial shiny skin, manually shine body) etc..As coating composition, ink composition, cement, surface Utilization example containing green tribo-luminescence fluorescent powder in coverture, can enumerate: financial institution, community organization, credit card company, The postals such as the crimping postcard sheet material used in the industry that circulates etc., containing green tribo-luminescence fluorescent powder in the bonding agent of stickup Post object；The furniture such as chair, bed；Flooring material, ceramic tile, wall material, prefabricated board material, paveio(u)r, timber steel are mixed The building materials such as solidifying soil；It is equipped on the automated navigation system device of vehicle；For operating the operating device of audio devices and air-conditioning etc.；Family The input units such as electrical article, portable machine, electronic computer；The images such as digital camera, CCD camera, film, photo, image Storage means etc..
It can produce new appearance and making green tribo-luminescence light-emitting phosphor, therefore also consider to toy, activity The expansion of the amusement commodity, daily necessity such as commodity.For example: the wind long narrow flag such as dynamic toy, kite, carp shape flag, swing, Quick sleigh, carrousel, bow and arrow etc.；Pass through wind-force while the Powerless type light emitting device (windbell etc.) of generation sound and light. The windmill of luminescent ball (golf, the ball of baseball, table tennis ball, ball of billiard ball etc.), luminous mechanism；Balloon；Laminated structure Object be paper, batch flute, paper folding, paper balloon, folding fan, New Year card, draw this；Sporting goods (jumping pole, fencing, bow and arrow etc. Long size objects etc.)；The score confirmation pressure sensitive sealant part of golf club, tennis court line tester, dynamic ornamentation body, Dynamic engraving, dynamic souvenir；Dynamic Display device；Shock-wave luminescence decoration device；The audio device such as loudspeaker, musical instrument are (small to mention The diaphragms such as the wind instruments such as the percussion instruments such as the stringed musical instruments such as qin, guitar, xylophone, drum, trumpet, flute, glass), tuning fork etc.；Movable quotient Product etc. entertain commodity；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；Change containing adhesion polymer Cosmetic compositions, the printed article that forgery can be distinguished under visual state and marketable securities, the printing containing stress irradiance particle Ink, bill, check, stock, bond, various security, exchange ticket, books certificate, the ticket of traffic organization, toll facility, project Middle lottery ticket of ballot certificate that admission ticket, lottery ticket, Public Physical Education are competed etc., bank note, identity card, ticket, the pass etc., passport, writing The printed article of organic ciphertext book seals sealing element etc..
Using shining along with stress, the photochemical catalyst for being attached to green tribo-luminescence phosphor surface is made to activate and obtain To, stress irradiance body-photochemical catalyst complex can be used for: antibacterial, sterilization, to the handrail of the treatment of non-human animal, vehicle The dirt purification of the antibacterial articles such as band, handle utilizes the energy of flow of the fluid of wall surface inside piping for being located at dark place etc. Purification.Stress irradiance substance activates the photocrosslinking agent in macromolecule resin, can also promote to be crosslinked by shining.
By the way that green tribo-luminescence fluorescent powder of the invention with being mixed in resin, can be formed resin combination of the invention Object.
In addition, being formed again by the way that other inorganic material or organic material are further added in resin combination of the invention Condensation material can also form stress irradiance 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 green tribo-luminescence fluorescent powder is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to Above-mentioned green 30~300 mass parts of tribo-luminescence fluorescent powder of 100 mass parts of resin compounding.Blend can be by using tapered mixed The mixing machines such as conjunction machine, V-Mixer, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill are set to make Oil/fat composition.
In addition, in the case where forming stress irradiance body by the resin combination, such as when obtaining the stress irradiance body of sheet, Such as relative to 100 parts by weight of Corvic, it is compounded above-mentioned green 50~200 mass parts of tribo-luminescence fluorescent powder, calcium-zinc Be 3~5 mass parts of stabilizer, 30~100 mass parts of dioctyl phthalate as plasticizer, with two-roller mill 150~ It is kneaded at 200 DEG C, so as to obtain the stress irradiance body with flexible sheet.
When obtaining the stress irradiance body of film-form, such as relative to 100 mass parts of pet resin, Above-mentioned green 20~50 mass parts of tribo-luminescence fluorescent powder are compounded, with double screw extruder, inflation processing machine at 250~300 DEG C Under be kneaded, formed, so as to obtain the stress irradiance body of film-form.
When obtaining the stress irradiance body of other shapes, such as relative to 100 mass parts of acrylic resin, it is compounded green friction 5~100 mass parts of luminescent phosphor are kneaded at 170~200 DEG C with double screw extruder, are formed, so as to obtain Band-like, plate, rodlike, partical stress irradiance body.In addition, by using injection (mo(u)lding) machine to pellet at 170~200 DEG C The stress irradiance body of shape carries out machine-shaping, the stress irradiance body of available three-dimensional shape.
When applying mechanical external force to the stress irradiance body, shone due to mechanically deform.
It as above-mentioned resin or other organic materials, can enumerate: resin as thermoplastic resin, thermosetting resin. As thermoplastic resin, for example: low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear, low density The polyethylene such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene- The polyamide such as the styrene polymers such as styrol copolymer (ABS resin) or copolymer, 6- nylon, 66- nylon, 12- nylon gather The acrylic resins such as amide imide, polyimides, polyetherimide, polyurethane, polymethyl methacrylate, poly- acetic acid second The fluororesin such as enester, vinyl-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), gather alkenyl aroma hydroxy-aromatic resin The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polylactic acid, bisphenol-A Be the polycarbonate such as polycarbonate, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, The polyacrylic acid such as polyacrylonitrile, polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, gather at styrene-acrylonitrile copolymer (AS resin) Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, liquid crystal polymer ethylene and propylene copolymer, ethylene or propylene With copolymer, ethylene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylene, 1- hexene, 4-methyl-1-pentene etc.) With the copolymer of monomer (vinyl acetate, acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl alcohol etc.) Deng.
Thermoplastic resin can be used alone or in combination of two or more kinds.It should be noted that thermoplastic resin is copolymerization It can be the copolymer of any forms such as random copolymer, block copolymer when object.As thermosetting resin, can enumerate: phenol Urea formaldehyde, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, Organic siliconresin, alkyd resin, polyimides, polyaminobismaleimide, casein resin, furane resins, polyurethane resin Deng.It can additionally enumerate: utilize ultraviolet light, the resin of radiation curing.
In turn, it can enumerate: natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethylene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
It in addition to this, can be by pigment, dyestuff, lubricant, antioxidant, ultraviolet absorbing agent, light stabilizer, antistatic Agent, fire retardant, fungicide, antibacterial agent, solidification catalyst, Photoepolymerizationinitiater initiater etc. and green tribo-luminescence fluorescence of the invention Powder is mixed together, and is shaped to rodlike, plate, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gel, sol form, suspension, aggregation, capsule-type.
As pigment, inorganic pigment, organic pigment can be enumerated.
As inorganic pigment, can enumerate: titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Kermes (red iron oxide (III)), cadmium red, ultramarine, dark blue, chrome oxide green, cobalt green, chocolate, titanium is black, synthesis is iron black, carbon black, Mica, the aluminium oxide covered by titanium oxide, iron oxide, mica, the glass flake, holographic pigment covered by titanium oxide, iron oxide Deng.In addition to this, it as metallic powdery pigment, can enumerate: aluminium powder, copper powders, powder of stainless steel, metallic colloid, conduct There are transparent emerylite, coloring mica, interference mica, interference aluminium oxide, the interference silica (interference glass) of interference effect Deng.
It as organic pigment, can enumerate: azo pigment (monoazo yellow, condensation azophosphine, azomethine Huang etc.), Huang Color iron oxide, titan yellow, pucherite, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Huang etc. Yellow uitramarine；The orange pigments such as permanent orange；Red iron oxide, naphthols AS system azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purples face such as cobalt violet, quinacridone violet, dioxazine violet Material；The blue pigments such as cobalt blue, phthualocyanine pigment (phthalocyanine blue etc.), anthracene indigo plant；The viridine greens such as phthalocyanine green, azo system disperse dyes, Organic dyestuff such as anthraquinone system disperse dyes etc..
As dyestuff, can enumerate: azo dyes, anthraquinone dye, bipseudoindoxyl dye, sulfur dye, triphenhlmethane dye, Pyrazolone dye, Stilbene dyestuff, diphenylmethane dye, Xanthene dyes, alizarin dyes, acridine dye, quinoneimine dye (piperazine Dyestuff, oxazine dye, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
It as antioxidant, can enumerate: hindered phenolic compound, phosphite ester based compound, phosphinate system chemical combination Object and thioether based compound etc..
It as hindered phenolic compound, can enumerate: alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyls -3 ', 5 '-di-tert-butyl-phenyls) propionic ester, 2- tert-butyl -6- (3 '-tert-butyls -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyl acrylate, 2,6- di-t-butyl -4- (N, N- dimethylaminomethyl) phenol, bis- uncle of 3,5- Butyl -4- benzylphosphonic acid diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl -6- tert-butyl phenol), 4,4 '-methylene-bis(2,6-di-t-butyl phenol)s, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylenes-bis- (6- Alpha-Methyl-benzyl-paracresol) 2,2 '-ethidines-bis- (4,6- di-t-butyl Phenol), 2,2 '-butanes-bis- (4- methyl-6-tert-butylphenol), 4,4 '-butanes bis- (3 methy 6 tert butyl phenols), Triethylene glycol-N- double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters, bis- [3- (the tertiary fourths of 3,5- bis- of 1,6-HD Base -4- hydroxy phenyl) propionic ester], bis- [2- tert-butyl -4- methyl 6- (3- tert-butyl -5- methyl -2- hydroxybenzyl) phenyl] it is right Bis- { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propiono the oxygroup] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (6- tert-butyl-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenol), bis- (3,5- di-t-butyl -4- hydroxyl benzyls Base) thioether, 4,4 '-two thio bis(2,6-di-butyl phenol)s, 4,4 '-three thio bis(2,6-di-butyl phenol)s, 2,2- Thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], bis- (just pungent sulfenyl) -6- (4- hydroxyls of 2,4- Base -3 ', 5 '-di-tert-butyl amidos) -1,3,5- triazine, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy group Cinnamamide), N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hydrazines of N ' -, (2- methyl -4- hydroxyl of 1,1,3- tri- Base -5- tert-butyl-phenyl) butane, 1,3,5- trimethyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid esters, 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono oxygroup] ethyl isocyanurate and four [methylene -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic esters] Methane etc..
As phosphite ester based compound, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid can be enumerated Three decyl esters, phosphorous acid trioctylphosphine ester, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid two are pungent Base mono-phemyol ester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, Phosphorous acid list octyl diphenyl, phosphorous acid three (diethyl phenyl) ester, phosphorous acid three (diisopropyl phenyl) ester, phosphorous acid three (di-n-butyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, phosphorous acid three (2,6- di-tert-butyl-phenyl) ester, two Stearyl pentaerythritol diphosphites, bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, bis- (tertiary fourths of 2,6- bis- Base -4- aminomethyl phenyl) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyl) pentaerythrite diphosphorous acids Ester, bis- { bis- (1- methyl-1-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, bis- (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..As other Phosphite ester based compound can be enumerated and be reacted with dihydric phenol class to the phosphite ester based compound with cyclic structure.
As phosphinate based compound, can enumerate: four (2,4- di-tert-butyl-phenyls) -4,4 '-biphenylene two are sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyl) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylens, four (2,6- di-tert-butyl-phenyl) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylens, the sub- phosphine of four (2,6- di-tert-butyl-phenyl) -3,3 '-biphenylene two Acid esters, bis- (2,4- di-tert-butyl-phenyl) -4- phenyl-phenyl phosphinates, bis- (2,4- di-tert-butyl-phenyl) -3- phenyl-benzene Base phosphinate, bis- (2,6- di-n-butyl phenyl) -3- phenyl-phenyl phosphinates, bis- (2,6- di-tert-butyl-phenyl) -4- benzene Base-phenylphosphite ester and bis- (2,6- di-tert-butyl-phenyl) -3- phenyl-phenyl phosphinates etc..
It as thioether based compound, can enumerate: thiodipropionate dilauryl, thio-2 acid two (tridecyl) Ester, thio-2 acid myristyl ester, thio-2 acid distearyl base ester, (the 3- lauryl propane thioic acid of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionate), pentaerythrite-four (3- octadecyl thiopropionate), season penta Tetrol four (3- myristyl thiopropionate) and pentaerythrite-four (3- stearyl-thio propionic ester) etc..As comprising ultraviolet The light stabilizer of light absorbers can be enumerated: benzophenone based compound, benzotriazole based compound, aromatic series benzoic ether Based compound, oxanilide based compound, cyanoacrylate based compound and the amine compound that is obstructed etc..
It as benzophenone based compound, can enumerate: benzophenone, 2,4-DihydroxyBenzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenones, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyl benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -5- sulphur Acyl group benzophenone, 5- chlorine-2-hydroxyl benzophenone, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -2 ' - Carboxyl benzophenone and 2- hydroxyl -4- (2- hydroxy-3-methyl-acryloxy isopropoxy) benzophenone etc..
It as benzotriazole based compound, can enumerate: 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- (3,5- bis- Tert-butyl -2- hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) benzotriazole, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) -5- chlorobenzotriazole, 2- (5- tert-butyl -2- hydroxy phenyl) benzotriazole, 2- [2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] -2H- benzotriazole and 2- (4 '-octyloxies -2 '-hydroxyl Phenyl) benzotriazole etc..
As aromatic series benzoic ether based compound, can enumerate: salicylic acid is to tert-butyl benzene base ester, salicylic acid to octyl Salicylic acids alkyl phenyl esters such as phenylester etc..
It as oxanilide based compound, can enumerate: 2- ethyoxyl -2 '-ethyloxanilide, 2- ethyoxyl -5- Tert-butyl -2 '-ethyloxanilide and 2- ethyoxyl -3 '-dodecyl butoxanilide etc..
It as cyanoacrylate based compound, can enumerate: cyano -3 ethyl -2-, 3 '-diphenylacrylate esters, 2- Ethylhexyl-cyano -3,3 '-diphenylacrylate ester etc..
It as the amine compound that is obstructed, can enumerate: 4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl keto Base -2,2,6,6- tetramethyl piperidine, 4- acryloxy -2,2,6,6- tetramethyl piperidine, 4- (phenylacetyl oxygroup) -2,2,6, 6- tetramethyl piperidine, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidine, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl oxygroup -2,2,6,6- tetramethyl piperidine, 4- benzyl oxygroup -2,2, 6,6- tetramethyl piperidine, 4- phenoxy group -2,2,6,6- tetramethyl piperidine, 4- (ethylcarbamoyl oxygroup) -2,2,6,6- tetramethyl Phenylpiperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidine, 4- (phenylcarbamoyl oxygroup) -2,2,6, 6- tetramethyl piperidine, bis- (2,2,6,6- tetramethyl -4- piperidyl) carbonic esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Bis- (2,2,6,6- tetramethyl -4- piperidyl) adipate esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) terephthalates, 1,2- bis- (2,2,6,6- tetramethyl -4- piperidyl oxygroup)-ethane, α, the bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen of α ' - Base)-paraxylene, bis- (2,2,6,6- tetramethyl -4- piperidyl)-toluylene -2,4- diurethanes, it is bis- (2,2, 6,6- tetramethyl -4- piperidyl)-hexa-methylene -1,6- diurethane, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic ester, three (2,2,6,6- tetramethyl -4- piperidyl)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono oxygroup } -2,2,6,6- tetramethyl piperidine and 1,2,3,4- butane tetracarboxylic acid and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidine and β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiro (5,5) of 2,4,8,10- 11 Alkane] dimethanol condensation product etc..
As antistatic agent, can enumerate: the toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are multiple Close the metal oxygens such as oxide, indium tin composite oxides, the electric conductivity indium oxide for being doped with Sn, F, Cl etc., tin oxide, zinc oxide Inorganic system's antistatic agent such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-laurel Amide propiono) the quaternary ammonium salts system, sulfonate based compound, alkyl phosphate such as trimethyl ammonium sulfate, neopelex The antistatic agent etc. of the organic systems such as based compound.
As fire retardant, can enumerate: bromide fire retardant, phosphorus flame retardant, chlorine-based flame retardant, triazine flame retardant, with And other inorganic flame retardants such as salt of phosphoric acid and piperazine etc..
As bromide fire retardant, can enumerate: brominated Polystyrene, brominated polyacrylate, brominated polyphenylether, bromination are double Phenol A type epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, using brominated bisphenol A as the polycarbonate oligomer of Material synthesis, two phthalimide chemical combination of bromination The compounds such as the brominated diphenyls base alkane such as object, bromination Biphenyl Ether and 1,2- bis- (penta-bromophenyl) ethane.Wherein it is possible to enumerate: poly- three The brominated Polystyrenes such as bromstyrol, poly- (dibromobenzene aether), decabrominated dipheny base ether, bis- (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethylene-is bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
It as phosphorus flame retardant, can enumerate: trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2- second Base hexyl) ester, tributoxyethyl phosphate, triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, phosphoric acid Three (isopropyl phenyl) esters, tricresyl phosphate (phenyl) ester, tricresyl phosphate naphthalene ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyl) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyl phosphate ester acid, 2- methacryloxyethyl phosphate ester acid, diphenyl -2- acryloyl Oxygroup ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyl phosphate, melamine phosphate, two (melamines) Phosphate, melamine pyrophosphoric ester, triphenylphosphine oxide, trimethylphenyl phosphine oxide, methanephosphonic acid diphenyl ester, phenyl-phosphonic acid two The phosphates such as ethyl ester, resorcinol Polyphenyl phosphate, 1,3- phenylene bis- (2,6- dimethylphenylphosphates), resorcinol Poly- (two -2,6- xylyls) phosphate, polymer with bis phenol A tolyl phosphate, bisphenol-A Polyphenyl phosphate, the poly- (2,6- bis- of quinhydrones Tolyl) condensed phosphoric acid esters such as the aromatic condensations phosphate such as phosphate and their condensation product etc..
It as chlorine-based flame retardant, can enumerate: five cyclodecane of pentachloro-, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..It as triazine flame retardant, can enumerate: melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- Diamino -6- nonyl -1,3,5- triazine, 2,4- diamino -6- hydroxyl -1,3,5- triazine, dihydroxy -1,3 2- amino -4,6-, 5- triazine, 2,4- diamino -6- methoxyl group -1,3,5- triazine, 2,4- diamino -6- ethyoxyl -1,3,5- triazine, 2,4- diamino Base -6- propoxyl group -1,3,5- triazine, 2,4- diamino -6- isopropoxy -1,3,5- triazine, sulfydryl -1 2,4- diamino -6-, 3,5- triazine and 2- amino -4,6- dimercapto -1,3,5- triazine etc..
It as the salt of phosphoric acid and piperazine, can enumerate: orthophosphoric acid piperazine, piperazine pyrophosphate and polyphosphoric acid piperazine etc..
As inorganic flame retardant, can enumerate: the antimonials such as antimony trioxide, Antimony pentachloride, zinc borate, Boratex, Aluminium hydroxide, magnesium hydroxide and red phosphorus etc..
As fungicide, can enumerate: the copper fungicides such as copper 8-hydroxyquinolinate, zineb (Zineb), maneb (Maneb) etc. have The organochlorines such as machine thiophanate fungicide, captan, Bravo system fungicide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximides system such as benzimidazole system fungicide, iprodione, vinclozolin, procymidone fungicide, furametpyr The morpholines system fungicide such as the phenylpyrroles such as amine system fungicide, fludioxonil system fungicide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidines system fungicide such as the methoxy acrylates such as ORIBRIGHT system fungicide, mepanipyrim, cyprodinil, pyrimethanil, The soil fungicides such as the ergosterol biosynthesis inhibitors such as triazolone, fluorine bacterium azoles, trichloronitromethane, PCNB and fluorine pyridine Bis- (acetyl bromide oxygroup) ethane of amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2-, cinnamic acid, acetic acid benzene Ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, the bromo- 3- itrile group propionyl of 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
It as antibacterial agent, can enumerate: make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Close inorganic system's powder obtained from object.It as load, can enumerate: zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..In addition it can enumerate: with phosphate, boric acid system, silicic acid system Be respectively in one kind or two or more glass as glass forming constituents of glass containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate: fatty acid, fatty acid metal salts, oxo fatty acid, paraffin, low molecular weight it is poly- Alkene, fatty acid amide, alkylenebisfatty amide, aliphatic ketone, fatty acid part are saponified ester, fatty acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethyl alcohol ester and modified organic silicon etc..
As fatty acid, can enumerate: oleic acid, stearic acid, lauric acid, hydroxy stearic acid, behenic acid, arachidonic acid, The fatty acid of the carbon numbers 6~40 such as linoleic acid, linolenic acid, ricinoleic acid, palmitinic acid, montanic acid and their mixture.As rouge Fat acid metal salt can be enumerated: sodium laurate, potassium laurate, Magnesium dilaurate, calcium laurate, zinc laurate, barium laurate, hard Resin acid sodium, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, behenic acid sodium, behenic acid potassium, behenic acid Alkali (soil) gold of the fatty acid of carbon numbers 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acid barium, montanic acid sodium and montanic acid calcium Belong to salt.
It as oxo fatty acid, can enumerate: 1,2- stearoxylic acid etc..
It as paraffin, can enumerate: the paraffin of 18 or more the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline.
It as the polyolefin of low molecular weight, can enumerate: polyethylene wax, maleic acid modified polyethylene wax, the poly- second of oxidized form Alkene wax, haloflex wax and the polyolefin below of polypropylene wax equimolecular quantity 5000.It, specifically can be with as fatty acid amide It enumerates: the fatty acid amide of 6 or more the carbon numbers such as oleamide, erucic amide, Shan Yu amide.
It as alkylenebisfatty amide, can enumerate: methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty amide of 6 or more the carbon numbers such as bis- (2- hydroxyethyl) stearmides.
It as aliphatic ketone, can enumerate: the aliphatic ketone of 6 or more the carbon numbers such as higher aliphatic ketone.As fatty acid moieties Divide saponification ester, can enumerate: partly-hydrolysed ester of montanic acid etc..
It as fatty acid low-carbon-ester, can enumerate: stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acid ester, arachidonate, montanate and isostearate etc..
It as polyol esters of fatty acids, can enumerate: glycerine tristearate, glycerine distearate, glycerine Monostearate, pentaerythritol tetrastearate, pentaerythrite tristearate, two myristinate of pentaerythrite, Ji Wusi Alcohol monostearate, pentaerythritol adipate stearate and anhydrous sorbitol Dan behenic acid ester etc..
As fatty acid polyglycol ethyl alcohol ester, can enumerate: cithrol, polytrimethylene diol fatty acid ester and Polypropylene glycol fatty acid esters etc..
As modified organic silicon, can enumerate: the alkoxy-modified organosilicon of organic silicon modified by polyether, higher fatty acids contains Having organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness of higher fatty acids has Machine silicon etc..
It as solidification catalyst, can enumerate: (peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and the organic peroxides, octyl acid tin, dibutyl such as azo-compound (azodiisobutyronitrile and azobisisovaleronitrile etc.) Tin two (2 ethyl hexanoic acid ester), dioctyl tin two (2 ethyl hexanoic acid ester), dioctyl tin diacetate esters, dibutyltindilaurylmercaptide cinnamic acid Ester, dioctyl tin dilaurate, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin fatty acid salt, 2 ethyl hexanoic acid Lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, 2 ethyl hexanoic acid lead lead octoate and four The inorganic acids such as Organometallic derivatives, hydrochloric acid, nitric acid, the sulfuric acid such as the metals such as n-butyl titanate and organic and inorganic acid salt, The sulfoacid compounds such as p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, sulfoacid compound Amine corrective, organic amines, phosphoric acid, the pyrophosphoric acid such as triethylamine etc., phosphate monoester or di-phosphate ester etc..As phosphate monoester, For example: mono-octyl phosphate, mono phosphoric acid ester propyl ester and mono phosphoric acid ester lauryl etc..As di-phosphate ester, for example: Dioctylphosphoric acid ester, phosphoric acid dipropyl and didodecyl phosphate etc..In turn, it can enumerate: single (2- (methyl) acryloxy second Base) phosphate cpds, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
It as Photoepolymerizationinitiater initiater, can enumerate: (2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propane - 1- ketone, 1- hydroxycyclohexylphenylketone, benzoin alkylether etc.), benzoyl formic acid ester compounds (methylbenzoyl formate Deng), thioxanthone compounds (isopropyl thioxanthone etc.), benzophenone cpd (benzophenone etc.), phosphate compound (1,3, 5- trimethylbenzoyl diphenyl phosphine oxide etc.) and benzil dimethyl ketal etc..
In turn, of the invention by the way that green tribo-luminescence fluorescent powder of the invention can also be made with coating is mixed in Stress irradiance coating composition.
Stress irradiance coating composition of the invention can be coated with the surface of other materials, to being coated with the luminescent material Material apply mechanical external force when, the luminous material layer of material surface is shone due to deformation.
In addition, the hair of the stress irradiance coating composition of the invention containing green tribo-luminescence fluorescent powder of the invention Brightness is high, therefore can carry out visual high coating.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root According to need can also contain: solvent, dispersing agent, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoaming agent, The coating such as antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and antibacterial agent Use additive.
As material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet light also can be used The various resins such as curable resin, radiation curing resin, for example: acrylic resin, alkyd resin, poly- ammonia Ester resin, polyester resin, amino resins etc., organosilicon acid esters, organic titanate etc..
It as ink film forming material, can enumerate: polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
It as solvent, can enumerate: aliphatic hydrocarbon, aromatic hydrocarbon (C7~10, such as toluene, dimethylbenzene and ethyl Benzene), ester or ether-ether (C4~10, such as methoxybutyl acetic acid esters), ether (single ethyl of C4~10, such as tetrahydrofuran, EG Ether, the single-butyl ether of EG, the monomethyl ether of PG and DEG single ethylether), (C3~10, such as methyl iso-butyl ketone (MIBK), two are just for ketone Butyl ketone), alcohol (C1~10, such as methanol, ethyl alcohol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohol), amide (C3~6, such as dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone), sulfoxide (C2~4, such as dimethyl sulfoxide) and their mixed solvent of more than two kinds, water or aforementioned mixed solvent.As dispersion Agent can enumerate: the formal of naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] as long as being macromolecule dispersing agent Woods condensation product, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2~4) carboxylic acid (Malaysia Acid/glycerol/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~10000) and polyethylene Alcohol (Mn2000~100000) etc..
As low molecule dispersing agent, following substances can be enumerated.
(1) poly (oxyalkylene) fundamental mode
Aliphatic alcohol (C4~30), [alkyl (C1~30)] phenol, aliphatic (C4~30) amine and aliphatic (C4~30) 1~30 mole of addition product of AO (C2~4) of amide.
As aliphatic alcohol, there are n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, octanol, dodecanol etc.；As (alkane Base) phenol, there are phenol, methylphenol and nonyl phenol etc.；As aliphatic amine, there are lauryl amine and methyl stearic amine etc.； With as aliphatic amide, there is stearmide etc..
(2) polyol type
The fatty acid (lauric acid, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, sorb Sugar alcohol and anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the fatty acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulphur of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 Acid esters alkali metal (same as described above) salt etc..
(5) sulfonate type
Sulfonate alkali metal (same as described above) salt of [alkyl (C1~30)] phenol (same as described above).
(6) phosphate type
The list of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 The salt [alkali metal (same as described above) salt, quaternary ammonium salt etc.] of phosphate or bisphosphate.
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and tertiary amine (the dimethyl stearyl of C4~30 Amine etc.)] inorganic acid (hydrochloric acid, sulfuric acid, the nitre of the monoesters of hydrochloride, triethanolamine and the fatty acid of C4~30 (same as described above) Acid and phosphoric acid etc.) salt.
(8) quaternary
The nothing of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 Machine acid (same as described above) salt etc..
It as inorganic dispersant, can enumerate: alkali metal (same as described above) salt and phosphate dispersing agent (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
It as filler, can enumerate: inorganic as the oxide system of representative using silica, aluminium oxide, zirconium oxide, mica The organic compounds such as the micro mist or acrylic resin, fluororesin of the non-oxidized substances based inorganic material such as object, silicon carbide, silicon nitride.Separately Outside, the metal powders such as aluminium, zinc, copper can also be added depending on the application.In turn, it as the concrete example of filler, can enumerate: dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based substance；Synthesize amorphous silica；Kaolinite, mica, talcum, wollastonite, asbestos, calcium silicates, silicic acid The silicates such as aluminium；The vitreums such as glass powder, glass marble, hollow glass ball, glass flake, bulb glass ball；Boron nitride, carbonization The non-oxidized substances based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, titanium carbide；Calcium carbonate； The metal oxides such as zinc oxide, aluminium oxide, magnesia, titanium oxide, beryllium oxide: barium sulfate, molybdenum disulfide, tungsten disulfide, fluorination The inorganic matters such as carbon；The metal powders such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Equal carbon body etc..
It as thickener, can enumerate: montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic fillers such as aluminium system thickener, methylcellulose, carboxymethyl cellulose, hexyl methyl cellulose, hydroxyethyl cellulose, hydroxyl The cellulose-based thickeners such as propyl cellulose, polyurethane resin system thickener, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene The polyethers trees such as the polyethylene-based thickener such as benzyl ether copolymer, polyethers dialkyl ester, polyethers dialkyl ether, the epoxy-modified object of polyethers The association thickeners such as rouge system thickener, urethane-modified polyether system, polyurethane resin system of polyether polyol system etc. are special The eggs such as the surfactants such as macromolecule nonionic thickener, nonionic system system thickener, casein, casein acid sodium, casein acid ammonium Acrylic thickeners such as white matter system thickener and mosanom etc..
As levelling agent, can enumerate: PEG type nonionic surfactant (nonyl phenol EO1~40 mole addition product, Stearic acid EO1~40 mole addition product etc.), polyol-based non-ionic surfactant (anhydrous sorbitol palm acid monoester, dehydration Sorbierite stearate monoesters, three ester of anhydrous sorbitol stearic acid etc.), fluorine-containing surfactant (perfluoroalkyl EO1~50 mole plus At object, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
Curing agent can be enumerated as the curing agent of polyalcohols: hexamethylene diisocyanate, trimethyl six Methylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, two isocyanide of diphenyl methane Acid esters, xylylene diisocyanate, hydrogenation xylylene diisocyanate, toluylene diisocya-nate, hydrogenation first generation Phenylene vulcabond, lysine diisocyanate, the nurate body of polyisocyanate compound, buret body, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propylene glycol, trimethylolpropane, by blocked polyisocyanic acid The monomers such as ester curing agent or mixture of more than two kinds, their polyalcohol addition product, their copolymer, block polymer etc. It like that at normal temperature being capable of cured isocyanates.It as the curing agent of epoxy resin, can enumerate: acid anhydrides, phenolic aldehyde tree Rouge, polyamide, amine additives, urea resin, melamine resin and isocyanates etc..
It as crosslinking agent, can enumerate: melamine resin, urea resin, polyisocyanate compound, block polyisocyanate cyanogen Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Rouge and hexamethoxy methylated melamine, N, N, N ', N '-tetrakis hydroxymethyl phosphonium succinamide, tetramethoxymethylization urine Element, 2,4,6- tetrakis hydroxymethyl phosphonium phenol etc. have the compound of hydroxymethyl and methoxy or ethoxyl methyl etc..
It as pigment, other than aforesaid pigments, can also enumerate: vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Equal vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid object, one hydrogen magnesium of phosphoric acid, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid object, phosphorus Sour magnesium cobalt eutectoid object, magnesium phosphate nickel eutectoid object, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid object, three polyphosphoric acid aluminum dihydrogens, three The phosphate metals such as polyphosphoric acid magnesium, the magnesia processed material of three polyphosphoric acid aluminum dihydrogens, the magnesia processed material of three polyphosphoric acid dihydro zinc The silica modified chemical combination of magnesium phosphate as the processed material of the magnesium-containing compound of salt and then silica modified magnesium phosphate etc. The phosphate-based rust resisting pigment such as object；The rust resisting pigment containing zinc ingredient such as trbasic zinc phosphate, magnesium handle three polyphosphoric acid aluminum dihydrogens, Calcium treatment Calcium phosphate etc. is without zinc rust resisting pigment；The calcium silicates such as the composite calcium silicate comprising calcium orthosilicate ingredient or calcium metasilicate ingredient；Calcium from The metal ion exchangeds silica such as son exchange silica, magnesium ion exchange silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoaming agent, for example: silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness are poly- The organic silicon-types such as siloxanes defoaming agent, mineral oil system defoaming agent, non-organic silicon polymer system defoaming agent, comprising changing selected from organic At least one kind of defoaming agent in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol comprising 18 or more carbon number Defoaming agent etc..
For antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and Antibacterial agent etc. can enumerate aforementioned substances.
Detailed description of the invention
Fig. 1 is 1 ~ 3 tribo-luminescence spectrogram of embodiment provided by the invention.
Fig. 2 is 4 ~ 6 tribo-luminescence spectrogram of embodiment provided by the invention.
Specific embodiment
Invention is further described in detail for 1-2 and specific embodiment with reference to the accompanying drawing.
Embodiment 1
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.98Al2SiO8: 0.01Eu2+, 0.01Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.98Al2SiO8: 0.01Eu2+, 0.01Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into Ma It is uniform that Nao mortar carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time according to total mass ratio 1:1 when grinding It is 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is sintered, sintering temperature is 1100 DEG C, and sintering time is 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/ 95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the sintered body of above-mentioned acquisition in Ma It is ground in Nao mortar to get a kind of green tribo-luminescence fluorescent powder.
Embodiment 2
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.95Al2SiO8: 0.04Eu2+, 0.01Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.95Al2SiO8: 0.04Eu2+, 0.01Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into Ma It is uniform that Nao mortar carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time according to total mass ratio 1:1 when grinding It is 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is sintered, sintering temperature is 1200 DEG C, and sintering time is 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/ 95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the sintered body of above-mentioned acquisition in Ma It is ground in Nao mortar to get a kind of green tribo-luminescence fluorescent powder.
Embodiment 3
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.92Al2SiO8: 0.04Eu2+, 0.04Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.92Al2SiO8: 0.04Eu2+, 0.04Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into Ma It is uniform that Nao mortar carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time according to total mass ratio 1:1 when grinding When being 0.5；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is sintered, sintering temperature is 1300 DEG C, and sintering time is 5 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/ 95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the sintered body of above-mentioned acquisition in Ma It is ground in Nao mortar to get a kind of green tribo-luminescence fluorescent powder.
Embodiment 4
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.88Al2SiO8: 0.08Eu2+, 0.04Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.88Al2SiO8: 0.08Eu2+, 0.04Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into Ma It is uniform that Nao mortar carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time according to total mass ratio 1:1 when grinding It is 0.5 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, have been dried under the conditions of 80 DEG C At rear taking-up sample and grinding distribution, uniformly mixed raw material is obtained；The uniformly mixed raw material is put into high temperature process furnances In be sintered, sintering temperature be 1300 DEG C, sintering time be 4 hours, heating rate be 10 DEG C/min, sintering atmosphere 5% H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；The sintered body of above-mentioned acquisition is existed It is ground in agate mortar to get a kind of green tribo-luminescence fluorescent powder.
Embodiment 5
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.84Al2SiO8: 0.08Eu2+, 0.08Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.84Al2SiO8: 0.08Eu2+, 0.08Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into Ma It is uniform that Nao mortar carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time according to total mass ratio 1:1 when grinding It is 1 hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry to complete under the conditions of 80 DEG C Sample and grinding distribution are taken out afterwards, obtain uniformly mixed raw material；The uniformly mixed raw material is put into high temperature process furnances It is sintered, sintering temperature is 1400 DEG C, and sintering time is 4 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/ 95%N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；By the sintered body of above-mentioned acquisition in Ma It is ground in Nao mortar to get a kind of green tribo-luminescence fluorescent powder.
Embodiment 6
A kind of green tribo-luminescence fluorescent powder, chemical composition Sr2.8Al2SiO8: 0.1Eu2+, 0.1Ga3+。
With the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr2.8Al2SiO8: 0.1Eu2+, 0.1Ga3+The proportion of middle each element accurately weighs each raw material；Above-mentioned raw materials are put into agate to grind It is uniform that alms bowl carries out ground and mixed, and dehydrated alcohol is added as abrasive media, milling time 1 according to total mass ratio 1:1 when grinding Hour；The pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours under the conditions of 80 DEG C, after the completion of dry Sample and grinding distribution are taken out, uniformly mixed raw material is obtained；By the uniformly mixed raw material be put into high temperature process furnances into Row sintering, sintering temperature are 1400 DEG C, and sintering time is 5 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95% N2Hydrogen nitrogen mixed gas, cool to room temperature with the furnace after the completion of sintering, obtain sintered body；The sintered body of above-mentioned acquisition is ground in agate It is ground in alms bowl to get a kind of green tribo-luminescence fluorescent powder.
Fig. 1 show the tribo-luminescence spectrogram of embodiment 1 ~ 3, it can be seen from the figure that embodiment 1 ~ 3 all has obviously Tribo-luminescence phenomenon, luminous peak position is near the green light of 535nm, active ions Eu2+With foreign ion Ga3+Doping it is dense Spending has great influence to the tribo-luminescence intensity of sample, from embodiment 1 and the comparison of embodiment 2 as can be seen that active ions Eu2+ Preferred concentration be 0.04, from embodiment 2 and the comparison of embodiment 3 as can be seen that foreign ion Ga3+Preferred concentration be also 0.04, by introducing Ga3+Ion is distorted lattice, generates defect level, can effectively enhance its tribo-luminescence effect.
Fig. 1 show the tribo-luminescence spectrogram of embodiment 4 ~ 6, it can be seen from the figure that embodiment 4 ~ 6 all has obviously Tribo-luminescence phenomenon, luminous peak position is near the green light of 538nm, active ions Eu2+With foreign ion Ga3+Doping it is dense Spending has great influence to the tribo-luminescence intensity of sample.Compared with embodiment 1 ~ 3, with active ions Eu2+The increase of concentration, Glow peak wavelength is slightly mobile to long wave direction.From embodiment 4 and the comparison of embodiment 5 as can be seen that foreign ion Ga3+It is preferred dense Degree is 0.04, is illustrated in Sr3-x-yAl2SiO8: xEu2+, yGa3+The Ga of certain content is introduced in fluorescent powder3+Ion can be effective Enhance its tribo-luminescence effect, also should not be too many but introduce content, preferred content is about 0.04.It can be with from embodiment 6 Find out, with active ions Eu2+With foreign ion Ga3+Doping concentration further increases, and tribo-luminescence effect further drops It is low.
The phenomenon that tribo-luminescence, is observed very early, but to the source of its excitation mechanism and excitation state, does not have also so far It determining completely, field personnel generally only do phenomenon description to tribo-luminescence, do not illustrate but its light sources and mechanism, Only think to influence that there are many triboluminescent factor, even if the substance of same element, in different preparation condition (such as concentration of element Proportion, sintering temperature, sintering time when refining substance), different pressure, under different frictional strengths, tribo-luminescent performance Difference it is also very big.Therefore, research tribo-luminescence is actually related with which factor, how to select most suitable experiment condition, has Synthesize to target tribo-luminescence body, there is important theoretical and practical significance.

Claims (2)

1. a kind of green tribo-luminescence fluorescent powder, which is characterized in that the chemical composition general formula of the fluorescent powder is Sr3-x- yAl2SiO8: xEu2+, yGa3+, the value range of x and y is respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1.
2. a kind of preparation method of green tribo-luminescence fluorescent powder, it is characterised in that the following steps are included:
(1) ingredient: with the SrCO of high-purity3、SiO2、Al2O3、Eu2O3And Ga2O is as raw material, according to chemical composition general formula Sr3-x-yAl2SiO8: xEu2+, yGa3+The proportion of middle each element accurately weighs each raw material；The value range of x and y is respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1；
(2) mixing: above-mentioned raw materials are put into agate mortar, and to carry out ground and mixed uniform, is added when grinding according to total mass ratio 1:1 For dehydrated alcohol as abrasive media, milling time is 0.5 ~ 1 hour；
(3) it dries: the pulp-like mixture of above-mentioned acquisition is placed in baking oven, heat preservation drying 4 hours, dry under the conditions of 80 DEG C Sample and grinding distribution are taken out after the completion, obtain uniformly mixed raw material；
(4) it is sintered: the uniformly mixed raw material being put into high temperature process furnances and is sintered, sintering temperature is 1100 ~ 1400 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, sintering It cools to room temperature with the furnace after the completion, obtains sintered body；
(5) it selects powder: the sintered body that step (4) obtain is ground in the agate mortar to get a kind of green friction hair Emitting phosphor.
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