CN104262780A - Preparation method of ultraviolet fluorescent-green plastic film by taking rare-earth phosphate glass as photochromic agent and application thereof in anti-counterfeiting aspects - Google Patents

Preparation method of ultraviolet fluorescent-green plastic film by taking rare-earth phosphate glass as photochromic agent and application thereof in anti-counterfeiting aspects Download PDF

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CN104262780A
CN104262780A CN201410472105.7A CN201410472105A CN104262780A CN 104262780 A CN104262780 A CN 104262780A CN 201410472105 A CN201410472105 A CN 201410472105A CN 104262780 A CN104262780 A CN 104262780A
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fluorescent
glass
phosphate glass
ultraluminescence
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CN104262780B (en
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张新林
许文才
罗世永
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Beijing Institute of Graphic Communication
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract

The invention relates to a preparation method of an ultraviolet fluorescent-green plastic film by taking rare-earth phosphate glass as a photochromic agent and application thereof in anti-counterfeiting aspects. Aiming at the problems of doped rare-earth fluorescent polymer materials, such as large polarity difference between an inorganic rare-earth fluorescent agent and a polymer material, rare-earth fluorescent concentration quenching, fluorescence stability and the like, the ultraviolet fluorescent-green plastic film has the characteristics that the phosphate glass is used as the substrate, Tb<3+> ion is used as a fluorescent activator, and Ce<3+> ion is used as a sensitizing agent, so that the fluorescent concentration quenching phenomenon is overcome, and the Eu addition amount and the fluorescence efficiency are increased through the synergistic effect of the phosphate glass matrix, Tb<3+> and Ce<3+> in the formula; glass fragments are pressed by using a melting method and an ice water mixture cooled glass tablet press, and then, the phosphate glass:Tb<3+>, Ce<3+> fluorescent powder with the granularity of being less than 300 nm is prepared through high-pressure grinding of an air-current mill; a surface modifier is added, fluorescent powder and polymer master-batch are molten and blended, and the plastic film obtained by being blown is white and transparent in the sun and emits beautiful green light under irradiation of ultraviolet light; and the plastic film has special transmission spectrum and can be used as an anti-counterfeiting packaging film, an anti-counterfeiting label printing substrate and an anti-counterfeiting safety line substrate.

Description

A kind of is the Ultraluminescence green plastics film preparation method of photochromic dose and the application in false proof thereof with RE phosphate glass
Technical field
The present invention relates to a kind of is the Ultraluminescence green plastics film preparation method of photochromic dose and the application in false proof thereof with RE phosphate glass, belongs to rare earth high polymer material field and anti-counterfeit field.
Background technology
The method added by rare earth element in macromolecular material is divided into two kinds substantially: (1) rare earth compound is distributed in monomer or polymkeric substance equably as doping agent, forms the rare earth high polymer existed with doping way, is called doping type rare earth high polymer.(2) first being synthesized by the mode of chemical bonding can the rare-earth complex monomer of polymerization reaction take place, then be polymerized with other organic monomers and obtain high-molecular copolymer, or on rare earth ion and macromolecular chain, ligand groups such as carboxyl, sulfonic group are obtained by reacting rare earth high polymer complex compound, and rare earth ion is present in macromolecular material with bonding pattern.Be called bonding type rare earth high polymer.
The fluorescent characteristic of rare earth element mainly comes from the f orbitals electronics of the underfilling of its internal layer.On the one hand, f orbitals electronics shield by 5s5p out-shell electron, by outer field affect little.Therefore, the fluorescence property that the content of rare earth doped compound in macromolecule matrix just can improve doping macromolecular material is improved.And on the other hand, due to the abundant f unoccupied orbital that rare earth ion has, ligancy higher (6-12), therefore during content of rare earth content height,, there is fluorescence intensity quenching phenomenon in easy formation ion cluster, is thus difficult to the rare earth high polymer material obtaining high fluorescent.Select suitable environment residing for the rare earth ion ligand of the rare earth ion (or be called matrix) to acquisition high fluorescence efficiency and high fluorescent very important.
Secondly, most rare earth compound polarity is large, and consistency between the less organic polymer of polarity is bad, and especially rare earth inorganics is little with resin affinity, causes the Polymer Mechanical degradation of doped with rare-earth elements, transparency reduction.The main method addressed this problem adopts effective technological method reduce rare earth mineral surfaces polarity and introduce coupling agent.
Rare earth luminous efficiency depends on the match condition of part lowest excited triplet energy level position and rare earth ion vibrational level, the excited triplet state energy level of phosphate glass matrix and Eu 3+excited level coupling better.Ce 3+mix the ultraviolet absorption substantially increasing sample altogether, the remarkable sensitization near-infrared luminous efficiency of sample.
Summary of the invention
The object of the invention is with simple formulation phosphate glass for matrix, with Tb 3+ion is photosensitizers, Ce 3+ion as sensitizing agent, by phosphate glass matrix, Tb 3+ion and Ce 3+synergistic effect, first prepare formation be beneficial to Tb 3+luminous phosphoric acid salt fluorescent glass.The characteristic airflow milling utilizing phosphate glass intensity low, crisp the is levigate glass powder being less than 300nm to median size, then obtains the green false-proof film of the Ultraluminescence with high-luminous-efficiency with plastic master batch melt blending blown film.
Concrete preparation method is as follows, and glass formula is converted as mass percent oxide compound is: P 2o 550-90; Li 2o 0-10; Na 2o 5-25; K 2o 0-15; Tb 2o 31-15%, Ce 2o 30.5-4%.Wherein P 2o 5by NH 4h 2pO 4or (NH4) 2hPO 4introduce; Li 2o is introduced by Quilonum Retard, Na 2o is introduced by sodium carbonate, K 2o is introduced by salt of wormwood, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove between 800-1100 DEG C after a certain temperature 10-30 minute, glass melt is cast in mixture of ice and water cooling be pressed into glass flake on roller tablet press, cooling the object of roller tablet press with mixture of ice and water is to improve cooling intensity, be easy to form amorphous glass, reduce glass phase-separating and form alkalimetal ion race tendency, reduce the possibility of fluorescence intensity cancellation.Then levigately in high pressure draft mill 300nm white fluorescent glass powder is less than to granularity.This glass powder, under 254nm and 365nm ultraviolet lighting, all produces the very strong green fluorescence of brightness.
By the fluorescent glass powder prepared, white oil, silane coupling agent, stearic acid or titanate coupling agent is selected to be surface-modifying agent, with common plastics, comprise polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch high pressure are blended, blended each constituent mass percentage formula scope is: granularity is less than the fluorescent glass powder of 300nm, 0.5-8%, coupling agent 0.5-2%, master batch 90-99%.The granulation of melting co-extrusion, blown film, obtain doped with rare-earth elements Tb 3+pP, PE, PVC, PC, PET Ultraluminescence film.These plastic films are about the same with normal film outward appearance in the sunlight, but show bright green fluorescence under ultraviolet lighting, as Anti-counterfeit plastic film base material, have special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
The invention has the beneficial effects as follows:
Phosphoric acid salt fluorescent glass powder prepared by the present invention, due to Tb 3+ion is by [PO 4] the saturated coordination of group, by Tb during high-temperature fusion 3+uniform ion distributes in the melt, Tb in glass 3+ion and Tb 3+between ion, spacing increases, and cannot be formed by Tb 3+the race that ion is formed, interionic energy trasfer of the same race does not occur, so there will not be concentration quenching under high doping, fluorescence intensity is with Tb 3+the increase of amount and increasing, on the one hand can improve the incorporation of effective Tb and not produce concentration quenching, can give full play to each Tb on the other hand 3+the fluorescent functional of ion, obtains the highest fluorescence intensity with minimum Tb incorporation, also reduces cost simultaneously.
Although f-f transition can be there is under light illumination in the f electronics in rare earth element, but uptake factor is little near ultraviolet region, luminous efficiency is low, and suitable phosphate glass matrix is high at extinction coefficient, after they are as ligand and rare-earth ion coordination, if its triplet excited state mates with the excited level of rare earth, then energy is passed to rare earth ion in non-radiative de excitation mode by its triplet excited state after absorbing ultraviolet region energy by ligand, the rare earth ion being in excited state returns low-lying level with radiation mode transition again, sends rare earth characteristic fluorescence.The energy of triplet state should higher than the energy of rare earth ion excited state, the excessive or too small fluorescence that all can not obtain high strength.With Tb 3+a small amount of Ce is added in ion-activated phosphate glass matrix 3+, Ce 3+tb is given by absorbed excitation energy transmission 3+, cause Ce 3+the luminous intensity quencher of self.Make excitation energy by Ce like this 3+be transferred to Eu 3+, effectively improve its fluorescence emission wavelengths scope, and improve its emission peak intensity, make it obviously strengthen in 618nm feature peak position intensity, reach enhancing fluorescent effect.
Utilize the formulating of recipe of phosphoric acid salt basic metal glass, lower the polarity of phosphate glass fluorescent material, add the way of coupling agent simultaneously, the polarity reduced between inorganic fluorescent glass powder and high molecule plastic is poor, increase the consistency of unorganic glass fluorescent material and polymer masterbatch melt blending, thus make the rare earth high polymer material of preparation have the high transparency and excellent mechanical strength.
Doping is a kind of easy, widely applicable and method that suitability is strong.Inorganic doping agent is compared with organic blended dose, and preparation technology is simple, to environment and body harmless.Overcome organic blended dose of existence and stability difference and the problem to human body and bad environmental.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Glass formula conversion is the oxide compound of mass percent: P 2o 560%; Li 2o 4%; Na 2o 15%; K 2o 15; Tb 2o 34%, Ce 2o 32%.Wherein P 2o 5by NH 4h 2pO 4introduce; Li 2o is introduced by Quilonum Retard, Na 2o is introduced by sodium carbonate, K 2o is introduced by salt of wormwood, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove, 900 DEG C of insulations are after 20 minutes, glass melt is cast in and is pressed into glass flake with mixture of ice and water cooling on roller tablet press, then levigately in high pressure draft mill be less than 300nm white fluorescent glass powder to granularity.
By the fluorescent glass powder prepared, white oil is selected to be coupling agent, respectively with common plastics, a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch is blended, blended formula is: granularity is less than the fluorescent glass powder of 300nm, 4%, surface-modifying agent 0.5%, plastic master batch 96.5%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Eu.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong green fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
Embodiment 2
Glass formula conversion is the oxide compound of mass percent: P 2o 575%; Na 2o 16%; Tb 2o 38%, Ce 2o 31%.Wherein P 2o 5by NH 4h 2pO 4introduce; K 2o is introduced by salt of wormwood, Na 2o is introduced by sodium carbonate, K 2o is introduced by salt of wormwood, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.In globars stove, 900 DEG C of insulations are after 20 minutes, are cast in by glass melt and are pressed into glass flake what cool with mixture of ice and water on roller tablet press, then levigately in high pressure draft grinds are less than 300nm white fluorescent glass powder to granularity.
By the fluorescent glass powder prepared, silane coupling agent KH570 is selected to be coupling agent, respectively with common plastics master batch, a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch is blended, blended mass percent formula is: granularity is less than the fluorescent glass powder of 300nm, 0.5%, tensio-active agent 1%, plastic master batch 98.5%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Eu respectively.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong red fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
Embodiment 3
Glass formula conversion is the oxide compound of mass percent: P 2o 580%; Na 2o 10%; Li 2o 5%; Tb 2o 33%, Ce 2o 32%.Wherein P 2o 5by NH 4h 2pO 4introduce; Na 2o is introduced by sodium carbonate, Tb 2o 3directly introduce with europiumsesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove, 900 DEG C of insulations are after 30 minutes, glass melt is cast in and is pressed into glass flake what cool with mixture of ice and water on roller tablet press, then levigately in high pressure draft mill be less than 300nm white fluorescent glass powder to granularity.
Be surface-modifying agent by the fluorescent glass powder prepared, stearic acid, respectively with common plastics, a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch is blended, blended formula is: granularity is less than the fluorescent glass powder 8% of 300nm, surface-modifying agent 2%, plastic master batch 90%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong green fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
Embodiment 4
Glass formula conversion is the oxide compound of mass percent: P 2o 578%; Na 2o 10%; K 2o 5; Tb 2o 36%, Ce 2o 31%.Wherein P 2o 5by NH 4h 2pO 4introduce; Na 2o is introduced by sodium carbonate, K 2o is introduced by salt of wormwood, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove, 1100 DEG C of insulations are after 10 minutes, glass melt is cast in and is pressed into glass flake what cool with mixture of ice and water on roller tablet press, then levigately in high pressure draft mill be less than 300nm white fluorescent glass powder to granularity.
By the fluorescent glass powder prepared, titanate coupling agent TC-114 is selected to be surface-modifying agent, respectively with common plastics, a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch is blended, blended formula is: granularity is less than the fluorescent glass powder 2% of 300nm, surface-modifying agent 1.5%, plastic master batch 96.5%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb respectively.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong green fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
Embodiment 5
Glass formula conversion is the oxide compound of mass percent: P 2o 570%; K 2o 23; Tb 2o 34%, Ce 2o 33%.Wherein P 2o 5by (NH 4) 2hPO 4introduce; K 2o is introduced by salt of wormwood, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove, 950 DEG C of insulations are after 10 minutes, glass melt is cast in and is pressed into glass flake what cool with mixture of ice and water on roller tablet press, then levigately in high pressure draft mill be less than 300nm white fluorescent glass powder to granularity.
By the fluorescent glass powder prepared, select silane coupling agent KH570 and common plastics, blended with a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch respectively, blended formula is: granularity is less than the fluorescent glass powder of 300nm, 1%, surface-modifying agent 1%, master batch 98%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Eu respectively.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong green fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.
Embodiment 6
Glass formula conversion is the oxide compound of mass percent: P 2o 590%; Na 2o 5.5%; Tb 2o 34%, Ce 2o 30.5%.Wherein P 2o 5by (NH 4) 2hPO 4introduce; Na 2o is introduced by sodium carbonate, Tb 2o 3directly introduce with terbium sesquioxide, Ce 2o 3direct cerous oxide is introduced.Glass batch is added in alumina crucible, in globars stove, 1100 DEG C of insulations are after 10 minutes, glass melt is cast in and cools be pressed into glass flake on roller tablet press with mixture of ice and water, then levigately in high pressure draft mill be less than 300nm white fluorescent glass powder to granularity.
By the fluorescent glass powder prepared, white oil is selected to be surface-modifying agent, respectively with common plastics, a kind of high pressure comprised in polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polycarbonate (PC), polyterephthalate (PET) master batch is blended, blended formula is: granularity is less than the fluorescent glass powder 5% of 300nm, surface-modifying agent 1%, plastic master batch 90-99%.The granulation of melting co-extrusion, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb respectively.These plastic films are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the very strong green fluorescence of brightness.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, realize novel antiforge function.Product can directly be used as after Anti-fake packaging film, compound as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Claims (6)

1. be the Ultraluminescence red plastics film preparation method of photochromic dose and the application in false proof thereof with RE phosphate glass, it is characterized in that, comprise the following steps:
The first step, with high-temperature melting method preparation containing rare earth Tb 3+and Ce 3+phosphate glass fluorescent material, to be filled a prescription each component and Eu by phosphate glass in formula 3+and Ce 3+synergistic effect, by mixture of ice and water cooled glass to roller tablet press, improve cooling intensity, overcome fluorescence intensity quenching phenomenon, improve rare earth element tb 3+addition and fluorescence efficiency, fluorescent material has special Ultraluminescence spectrum;
Second step, by phosphate glass fluorescent material and conventional macromolecular material master batch under the condition of adding surface-modifying agent, melt blending preparation has the fluorescent green plastics film of special Ultraluminescence spectrum, overcome the impact of polymer base material on rare-earth fluorescent, Ultraluminescence luminous efficiency is high, and fluorescence is strong;
3rd step, using green for Ultraluminescence film directly as Anti-fake packaging film with as antifalsification label printing element with as anti-fake safety line base material.
2. according to claim 1 a kind of take RE phosphate glass as the green plastics film preparation method of Ultraluminescence of photochromic dose, it is characterized in that the preparation method of the phosphate glass glass described in the first step is: glass formula conversion for mass percent oxide compound is: P 2o 550-90; Li 2o 0-10; Na 2o 5-25; K 2o 0-15; Tb 2o 31-15%; Ce 2o 30.5-4%; Various raw material is pressed component design metering, after Homogeneous phase mixing, a certain temperature 10-30 minute in 800-1100 DEG C, after glass metal being cast in the pair roller tabletting machine with mixture of ice and water cooling, being broken to mean particle size by airflow milling high-pressure powder and being less than 300nm.
3. according to claim 1 a kind of take RE phosphate glass as the green plastics film preparation method of Ultraluminescence of photochromic dose, it is characterized in that the polymer master batch described in second step, refer to any one in polypropylene (PP) or polyethylene (PE) or polyvinyl chloride (PVC) or polycarbonate (PC) or polyterephthalate (PET).
4. according to claim 1 a kind of take RE phosphate glass as the green plastics film preparation method of Ultraluminescence of photochromic dose, it is characterized in that the surface-modifying agent described in second step, refer to the one in white oil or silane coupling agent or stearic acid or titanate coupling agent.
5. according to claim 1 a kind of take RE phosphate glass as the green plastics film preparation method of Ultraluminescence of photochromic dose, it is characterized in that the blended each constituent mass percentage formula scope of melt blending described in second step is: granularity is less than the fluorescent glass powder of 300nm, 0.5-8%, surface-modifying agent 0.5-2%, master batch 90-99%.
6. according to claim 1 a kind of be the Ultraluminescence green plastics film preparation method of photochromic dose and the application in false proof thereof with RE phosphate glass, it is characterized in that these plastic films are about the same with normal film outward appearance in the sunlight, white clear, but under 254nm and 365nm ultraviolet lighting, all produce the very strong red fluorescence of brightness.And there is special visible light-transmissive spectrum, directly as Anti-fake packaging film or as antifalsification label printing element or as anti-fake safety line base material.
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CN111545077A (en) * 2020-06-15 2020-08-18 黄淮学院 Preparation method and application of rare earth complex-containing mixed matrix film

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104575256A (en) * 2015-01-19 2015-04-29 黑龙江铭翔科技有限公司 Making method of fluorescent anti-counterfeit label
CN105398253A (en) * 2015-09-06 2016-03-16 深圳市天兴诚科技有限公司 Anti-counterfeiting material and preparation method thereof
CN105398254A (en) * 2015-12-05 2016-03-16 深圳市天兴诚科技有限公司 Anti-counterfeiting material and preparation method thereof
CN105538948A (en) * 2015-12-05 2016-05-04 深圳市天兴诚科技有限公司 Anti-counterfeiting material and preparation method thereof
CN108299729A (en) * 2017-12-27 2018-07-20 浙江普利特新材料有限公司 A kind of inexpensive, high-efficiency fluorescence polypropylene functional agglomerate and its composite material preparation method
CN110128730A (en) * 2019-05-14 2019-08-16 安徽银泰塑业有限公司 A kind of light sensation anti-fake bottle lid and its manufacturing method
CN111545077A (en) * 2020-06-15 2020-08-18 黄淮学院 Preparation method and application of rare earth complex-containing mixed matrix film

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