CN102354473B - High-brightness long-afterglow luminescent indicator plate and preparation method thereof - Google Patents
High-brightness long-afterglow luminescent indicator plate and preparation method thereof Download PDFInfo
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- CN102354473B CN102354473B CN 201110334582 CN201110334582A CN102354473B CN 102354473 B CN102354473 B CN 102354473B CN 201110334582 CN201110334582 CN 201110334582 CN 201110334582 A CN201110334582 A CN 201110334582A CN 102354473 B CN102354473 B CN 102354473B
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Abstract
The invention discloses a high-brightness long-afterglow luminescent indicator plate and a preparation method thereof. The preparation method comprises the following steps: pasting a reflective film on the front face of a substrate; spray-printing a luminous coating on the reflective film so as to form a graphical silkscreen; coating a diphenylethene-biphenyl sodium disulfonate fluorescent layer on the silkscreen; and coating a radiation-proof UV (ultraviolet) gloss oil protective layer on the reflective film which is not covered with graphs as well as the fluorescent layer. The preparation method of the luminous coating comprises the following steps: firstly pouring one third of a cristobalite transparent filler into a mixing tank, adding special light-transmitting resin, PE (polyethylene) resin and dioctyl phthalate (DOP), and then evenly stirring; and sequentially adding pigment, a nano rare-earth luminescent material, glass microspheres and the residual cristobalite transparent filler while stirring, and then evenly stirring for use. For the high-brightness long-afterglow luminescent indicator plate obtained by the preparation method, the brightness can reach 19,800mcd/m<2>, luminescence time can reach 10-14 hours in the case of single light absorption for 30 minutes, the minimum retro-reflection coefficient is cd.1*x<-1>m<-2> for various colors, the observation angle is 0.2 degree, and the incident angle is -4 degree. The high-brightness long-afterglow luminescent indicator plate has the advantages of endless cyclic energy storage, aging resistance, corrosion resistance, flame retardance, no toxicity, no harm, no radiation and energy conservation and is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of energy-accumulating luminous label, be specifically related to a kind of high brightness, long-afterglow illuminating signboard, the invention still further relates to the preparation method of this luminescence scutcheon.
Background technology
Label relates to the important medium in personal safety as well as the property safety field as safety, traffic, caution, prompting, fire-fighting etc., playing the part of indispensable role in productive life.From the angle of caution, prompting, label requires to have eye-catching understandable, long-lived characteristics usually.Present most sign manufacturing adopts common reflective membrane technology, and display effect is general, and display effect is poorer under the dark environment such as night and misty rain weather, needs just can distinguish under strong illumination.Because manufacture craft is coarse, poor with material, a lot of labels come into operation namely begin soon to fade, get rusty, image comes off.Aging rapidly under solar radiation, wind and weather condition, until corrosion damage, thoroughly lose caution, suggesting effect, both brought great dangerous hidden danger to lives and properties, increase again maintenance cost, therefore in the urgent need to employing new technology, guarantee that label can play the effect of caution, prompting really under various environment.
Energy-accumulating luminous label can improve the visual not enough shortcoming of common label, make people just can clearly recognize label without light-illuminating under the poor environment of rain, mist, dark, night visual isopter resolving ability, especially mountain area, township road lack lighting installation night, common Scutcheon coating does not have the light-illuminating can not be reflective, make pedestrian and bicycle end user can't see sign label, cause dangerous the generation, bring hidden danger to traffic safety, therefore be necessary to develop the label of suitable luminescent materials.The energy-storing self-luminescent label can active illuminating on the basis of satisfying the reflective requirement of label, has initiatively identifiability.Its visuality is better than common label greatly under gauge without light source, darker environment, allows the people can clear identification.The energy-storing self-luminescent label need not external power supply, but infinite loop is luminous, is energy saving environmental protection product of new generation, is the developing direction that the national policy emphasis is supported.
Chinese patent CN1108413 discloses a kind of luminescence scutcheon and preparation method thereof, adopts electrostatic painting process to make protective layer on card in one's hand surface, then is becoming hide chromatograph and luminescent layer with silk screen process dry powder through high-temperature firing at character code pattern position.The present invention adopts white resin dry powder to be fired into the screening chromatograph.Adopt luminescent material to become luminescent layer with the transparent resin mixed sintering, utilize light shield layer to hide the dark brown protective layer, bringing into play to greatest extent incandescnet particle effect in luminescent layer, and keep incandescnet particle not with the outside air contact with moisture, strengthen the luminescence scutcheon luminous intensity.But still there is the problem that luminous intensity is low, fluorescent lifetime is short.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of energy-storing self-luminescent, long-lived high-brightness long-afterglow luminescent indicator plate.
For solving the problems of the technologies described above, the technical scheme that high-brightness long-afterglow luminescent indicator plate of the present invention adopts is: it comprises substrate, the front of described substrate is provided with reflective membrane, reflective membrane is provided with the figure silk-screen layer, establish again stilbene biphenyl sodium disulfonate fluorescence coating on silk-screen layer, scribble radiation proof UV gloss oil protective layer on figure and the reflective membrane that is not hidden by figure and fluorescence coating; Described silk-screen layer is a kind of luminous paint, and this luminous paint comprises following material by weight percentage:
Printing opacity is resin dedicated: 15～20;
PE resin: 0.8～1.2;
Dioctyl phthalate: 0.8～1.2;
Cristobalite transparent filler: 40～45;
The glass microballoon of granularity＜150 μ m: 18～20;
EVA： 0.6～1.1；
Nano-scale Rare-earth Luminescent Materials: 14～20.
The present invention also provides the preparation method of above-mentioned high-brightness long-afterglow luminescent indicator plate, the steps include:
A) luminous paint preparation: at first pour 1/3rd cristobalite transparent filler into mixing kettle, add then that printing opacity is resin dedicated, PE resin, dioctyl phthalate, stir; After adding successively again pigment, Nano-scale Rare-earth Luminescent Materials, glass microballoon and remaining cristobalite transparent filler to stir under stirring condition, go out still and pack standby;
B) luminescence scutcheon preparation: geomery in accordance with regulations cuts substrate, the polishing burr; Reflective membrane is cut into size of substrate, is flattened on substrate front side; With the web plate centrally aligned substrate center of having carved figure, the luminous paint that has prepared is evenly sprayed by web plate be imprinted on reflective membrane, reaction forms the luminous pattern silk-screen layer through aggregation deposition, more even spraying stilbene biphenyl sodium disulfonate forms fluorescence coating on silk-screen layer; On figure and the reflective membrane that is not hidden by figure and fluorescence coating evenly spraying one deck radiation proof UV gloss oil form protective layer, then desiccant dehumidification, check, packing.
Label of the present invention adopts substrate, reflective membrane, silk-screen layer, fluorescence coating and protective layer, silk-screen layer is printed as figure by luminous paint, and contain Nano-scale Rare-earth Luminescent Materials in luminous paint, therefore, label of the present invention has the self luminous characteristic of high-brightness long persistence, and anti-aging, fire-retardant, anticorrosive, anti-oxidant, durable in use.In label autoluminescence spectrum, without radiation such as ultraviolet ray, infrared rays, dazzle is little; Not containing any radioelement and heavy metal, do not pollute the environment, can not damage health, is new generation of green environment-friendly and energy-efficient product.Label of the present invention can be widely used in safe, caution, the prompting in the fields such as traffic, fire-fighting, electric power, municipal administration, factories and miness, dwelling house, sight spot, military affairs, can play the effect of instant floor light in electric power supply inconvenience or the zone that often has a power failure.
The preparation method of label of the present invention is simple, practical, and use occasion that can be different according to label adopts different substrate materials to make, as various sheet metals, flame-proof PVC plate, plastic base, rubber, pottery, acrylic board, tempered glass, film etc.Adopt Nano-scale Rare-earth Luminescent Materials and macromolecule resin to adopt in-situ inserted technology, implement link aggregation (HSL) and aggregation deposition (HSCVD), produce the energy-accumulating luminous label of high brightness, long afterglow.The luminosity of label is up to 19800mcd/ ㎡, and fluorescent lifetime reaches 10-14 hours under 30 minutes prerequisites of single extinction.Each color minimal reverse reflection coefficient cd1x 1m 2,0.2 ° of observation angle, incident angle-4 °.The infinite loop accumulation of energy, anti-aging, corrosion-resistant, fire-retardant, nontoxic, radiationless, energy-conserving and environment-protective.
Description of drawings
Fig. 1 is the exploded perspective view of luminescence scutcheon of the present invention;
Fig. 2 is the assembling schematic diagram of luminescence scutcheon of the present invention;
Fig. 3 is the hole transfer mechanism figure of luminous paint in the present invention;
Fig. 4 is the spectral distribution graph of luminous paint in the present invention.
Embodiment
Share the track road signs as example explanation the present invention take craspedodrome and right-hand rotation.By Fig. 1 and Fig. 2 as seen, high-brightness long-afterglow luminescent indicator plate of the present invention comprises substrate 1, the front of substrate 1 is provided with reflective membrane 2, reflective membrane 2 is provided with figure silk-screen layer 3, establish stilbene biphenyl sodium disulfonate fluorescence coating 4 on silk-screen layer 3, remaining reflective membrane 2 and fluorescence coating 4 are provided with radiation proof UV gloss oil protective layer 5 again.
Label of the present invention is made according to geomery and the graphic designs of national relevant industries standard-required.Described figure is word, figure or its combination.Concrete preparation method is:
A) luminous paint preparation: the cristobalite transparent filler that at first takes 2.8 ㎏ is poured mixing kettle into, then adds resin dedicated 1.8 ㎏ of printing opacity and PE resin 0.1 ㎏, dioctyl phthalate 0.1 ㎏, stirs; After adding successively again pigment, Nano-scale Rare-earth Luminescent Materials 1.8 ㎏, glass microballoon 1.8 ㎏ and 1.4 ㎏ cristobalite transparent fillers to stir under stirring condition, go out still and pack standby;
B) luminescence scutcheon preparation: geomery in accordance with regulations cuts substrate 1, the polishing burr; Reflective membrane 2 is cut into substrate 1 size, is flattened on substrate 1 front; With web plate centrally aligned substrate 1 center of having carved figure, the luminous paint that has prepared is evenly sprayed by web plate be imprinted on reflective membrane 2, reaction forms luminous pattern silk-screen layer 3 through aggregation deposition, more only luminous pattern is regional at silk-screen layer 3() upward evenly spraying stilbene biphenyl sodium disulfonate forms fluorescence coating 4; On the reflective membrane 2 that is not hidden by figure and fluorescence coating 4 evenly spraying one deck radiation proof UV gloss oil form protective layer 5, then desiccant dehumidification, check appearance graphic, geomery, function (darkroom check) are packed.
Raw material in the present invention is the commercially available prod, wherein: the cristobalite transparent filler is the high-purity silicon dioxide product that the cristobalite ore deposit extract, EVA is vinyl-vinyl acetate copolymer, Nano-scale Rare-earth Luminescent Materials is novel rare-earth element aluminum Barbiturates material, and Science and Technology Ltd. produces by credit Dexing, Shenzhen.
The luminous paint that the present invention uses is to adopt Nano-scale Rare-earth Luminescent Materials formulated, and luminosity is up to 19800mcd/ ㎡, and fluorescent lifetime reaches 10-14 hours under 30 minutes prerequisites of single extinction.The nano rare earth raw material is mainly the light-accumulating luminous material of rear-earth-doped aluminate, has extremely strong extinction-hold light-luminous power, the serviceable life (〉=15 years) of extremely growing, can repeatedly absorb-store-launch visible light, (200-450nm), excitation source is easy to get excitation wavelength range, sunshine or common daylight lamp get final product, by absorbing ultraviolet or visible light, be stored in lattice after making light energy conversion, can be again in the dark luminous energy and luminous with Conversion of Energy.With Eu
2+The MAl2O4:Eu that activates
2+, RE
3+(M=alkali earth metal, RE=rare earth element) for the hole transfer mechanism of the new type long-persistence luminescent material of representative referring to Fig. 3.
As seen from Figure 3, due to Eu
2+And RE
3+Introducing, produce defective in crystal lattice, the depth different local level has just been arranged.At first, when luminophor is subjected to ultraviolet light or solar light irradiation, luminescent center Eu
2+Ground state 4f7(8S) the Electron absorption photon is to excited state 4f65d1 transition (1), just produced an electron vacancy (being the hole) on the 4f track, gets back to ground state when be combined in the hole when electronics jumps again, just produced luminous (2).Be in electronics in valence band and can obtain energy from environment and fill up hole on the 4f track, produce simultaneously new hole on valence band, this process is equivalent to the hole and transfers to valence band and cause Eu
2+Become Eu
+(3).Move in valence band in hole in valence band, then by RE
3+Defective can be with to capture and make RE
3+Change RE into
4+(4).Along with prolongation and the thermal perturbation of time, by RE
3+The hole of capturing obtains enough energy and comes back to valence band (5) from environment.Migration is continued in the hole of getting back in valence band, as close Eu
+Local energy level the time again can be by Eu
+Capture and discharge with the electron recombination of 4f65d1 configuration photon and form twilight sunset (6).The hole metastasis model is thought, RE
3+Effect be exactly the hole of capturing in valence band, change quantity and the concentration in hole, then the hole is emitted in time prolongation and thermal perturbation, makes luminescent center trapped hole again, and is luminous with electron recombination, thereby extends after time and strengthen afterglow intensity.This novel nano rare earth luminescent material is compared with traditional zinc sulphide series luminescent powder, has stable chemical nature, and light-accumulated luminous conversion efficiency is high, and is nontoxic, harmless, "dead", and production run also unharmful substance produces.
Through Anhui Province's product quality inspection Spot detection, luminous paint meets GB/T 13306-2011 national standard.Visible light is the appreciable part of human eye in electromagnetic wave spectrum, and visible spectrum does not have accurate scope; The appreciable electromagnetic wavelength of common people's eyes is between 400～700 nm, and the human eye of twenty-twenty vision is the most responsive to the electromagnetic wave that wavelength is about between 500～560 nm.Referring to the spectral distribution graph of Fig. 4, its luminescent light wave peak value is: 524nm, luminous radiance: 9.08 * i 0-6 (W/SR/M' ').Its luminous light wave just human eye to the most responsive wavelength coverage of light wave in.
This luminous paint is a kind of environmental protection, nontoxic, radiationless, pollution-free product.Detect through Anhui Province inspection center of technical quality surveillance authority, meet GB/T 6566-2001 standard, reach the category-A finishing material, detected value is lower 50 times than standard value.Without harm, can directly contact skin for human body.
The parameters of label of the present invention is:
1, product composition: base material, Nano-scale Rare-earth Luminescent Materials;
2, luminosity: 19800mcd/ ㎡;
3, fluorescent lifetime: single extinction 30 minutes, can be at the dark place luminous 10-14 hours;
4, glow color: gold-tinted, blue light etc.;
5, material hardness: soft or hard all can;
6, reflective parameter: each color minimal reverse reflection coefficient cd1x 1m 2,0.2 ° of observation angle, incident angle-4 °;
7, properties of product: infinite loop accumulation of energy, anti-aging, corrosion-resistant, fire-retardant, nontoxic, radiationless, energy-conserving and environment-protective;
8, installation method: inserted, riveted type, suspension type, adherent etc.
Claims (2)
1. high-brightness long-afterglow luminescent indicator plate, comprise substrate, it is characterized in that: the front of described substrate (1) is provided with reflective membrane (2), reflective membrane (2) is provided with figure silk-screen layer (3), establish stilbene biphenyl sodium disulfonate fluorescence coating (4) on silk-screen layer (3), figure and the reflective membrane (2) and the fluorescence coating (4) that are not hidden by figure are provided with radiation proof UV gloss oil protective layer (5) again; Described silk-screen layer is a kind of luminous paint, and this luminous paint comprises following material by weight percentage:
Printing opacity is resin dedicated: 15～20;
PE resin: 0.8～1.2;
Dioctyl phthalate: 0.8～1.2;
Cristobalite transparent filler: 40～45;
The glass microballoon of granularity＜150 μ m: 18～20;
EVA：0.6～1.1；
Nano-scale Rare-earth Luminescent Materials: 14～20;
Described Nano-scale Rare-earth Luminescent Materials is novel rare-earth element aluminum Barbiturates material.
2. the preparation method of a high-brightness long-afterglow luminescent indicator plate as claimed in claim 1, the steps include:
A) luminous paint preparation: at first pour 1/3rd cristobalite transparent filler into mixing kettle, add then that printing opacity is resin dedicated, PE resin, dioctyl phthalate, stir; After adding successively again pigment, Nano-scale Rare-earth Luminescent Materials, glass microballoon and remaining cristobalite transparent filler to stir under stirring condition, go out still and pack standby;
B) luminescence scutcheon preparation: geomery in accordance with regulations cuts substrate (1), the polishing burr; Reflective membrane (2) is cut into substrate (1) size, is flattened on the positive formation of substrate (1); With web plate centrally aligned substrate (1) center of having carved figure, the luminous paint that has prepared is evenly sprayed by web plate be imprinted on reflective membrane (2), reaction forms luminous pattern silk-screen layer (3) through aggregation deposition, then forms fluorescence coating (4) at the upper evenly spraying of silk-screen layer (3) stilbene biphenyl sodium disulfonate; The upper evenly spraying of figure and the reflective membrane (2) that do not hidden by figure and fluorescence coating (4) one deck radiation proof UV gloss oil forms protective layer (5), then desiccant dehumidification, check, packing.
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| CN 201110334582 CN102354473B (en) | 2011-10-31 | 2011-10-31 | High-brightness long-afterglow luminescent indicator plate and preparation method thereof |
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| CN 201110334582 CN102354473B (en) | 2011-10-31 | 2011-10-31 | High-brightness long-afterglow luminescent indicator plate and preparation method thereof |
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| CN102354473B true CN102354473B (en) | 2013-06-12 |
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| CN105696327B (en) * | 2016-02-25 | 2018-02-02 | 东莞市联洲知识产权运营管理有限公司 | A kind of environmentally friendly universal fluorescent brightening agent and preparation method thereof |
| CN105802475A (en) * | 2016-05-27 | 2016-07-27 | 温州雏鹰科技有限公司 | Light-storing long-afterglow light-emitting coating |
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| CN106952590A (en) * | 2017-05-14 | 2017-07-14 | 安徽昂然节能环保科技有限公司 | A kind of manufacture method of night bright reflecting long-afterglow label |
| CN106960639A (en) * | 2017-05-14 | 2017-07-18 | 安徽昂然节能环保科技有限公司 | A kind of night bright reflecting long-afterglow label |
| CN107945690B (en) * | 2017-11-29 | 2020-03-06 | 四川三盛恒业科技有限公司 | Long-afterglow self-luminous public signboard and manufacturing method thereof |
| CN108145958B (en) * | 2017-12-26 | 2020-12-29 | 鲁毅 | Method for manufacturing high-weather-resistance fluorescent color pattern of plastic reflective substrate |
| CN110264910A (en) * | 2019-07-03 | 2019-09-20 | 东莞市钜欣电子有限公司 | A kind of light-emitting indicating sign board |
| CN114241948A (en) * | 2021-12-20 | 2022-03-25 | 湖南鼎一致远科技发展有限公司 | Electroluminescent signboard and preparation method thereof |
| CN115323582A (en) * | 2022-08-12 | 2022-11-11 | 龚美纯 | Jacquard luminous fabric and preparation method thereof |
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| CN1396570A (en) * | 2001-07-12 | 2003-02-12 | 林南 | Reflecting long-afterglow luminous marker |
| CN101886745A (en) * | 2010-06-29 | 2010-11-17 | 彩虹集团公司 | Long-persistence fluorescent source and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143463A (en) * | 1995-06-13 | 1997-06-03 | Beijing City Fengtai Kogyo Toso Horyosho | High-luminance long-afterglow phosphorescent material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396570A (en) * | 2001-07-12 | 2003-02-12 | 林南 | Reflecting long-afterglow luminous marker |
| CN101886745A (en) * | 2010-06-29 | 2010-11-17 | 彩虹集团公司 | Long-persistence fluorescent source and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| JP特开平9-143463A 1997.06.03 |
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