CN110241608A - A kind of luminescent fibre and the preparation method and application thereof - Google Patents
A kind of luminescent fibre and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110241608A CN110241608A CN201910638793.2A CN201910638793A CN110241608A CN 110241608 A CN110241608 A CN 110241608A CN 201910638793 A CN201910638793 A CN 201910638793A CN 110241608 A CN110241608 A CN 110241608A
- Authority
- CN
- China
- Prior art keywords
- doughnut
- luminescent
- luminescent fibre
- fibre
- perovskite
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- 239000000835 fiber Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 235000012489 doughnuts Nutrition 0.000 claims abstract description 80
- 239000000126 substance Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims description 44
- 150000001768 cations Chemical class 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 40
- -1 halide ion Chemical class 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 16
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 16
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 16
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005642 Oleic acid Substances 0.000 claims description 16
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 16
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 229920001131 Pulp (paper) Polymers 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 6
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000001409 amidines Chemical class 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000012209 synthetic fiber Substances 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940006460 bromide ion Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001215 fluorescent labelling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- 241000122205 Chamaeleonidae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/405—Marking
- B42D25/415—Marking using chemicals
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- B42D2033/14—
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to luminescent material preparation technical fields, provide a kind of luminescent fibre, including doughnut and the luminescent substance being carried in the doughnut.A kind of preparation method of luminescent fibre, comprising: luminescent substance is carried in doughnut.The luminescent substance of the load is not easily to fall off, and luminescent fibre stability is good.Luminescent fibre makes the long service life of anti-fake product and fluorescent product when can be applied in anti-fake product and fluorescent product.
Description
Technical field
The present invention relates to luminescent material preparation technical fields, in particular to a kind of luminescent fibre and preparation method thereof
With application.
Background technique
Currently, the fast development with economy with the continuous progress of science and technology, for novel green, free of contamination luminescent fibre
Demand it is further strong.Since the plasticity of luminescent fibre is strong, arrangement diversity, good luminous performance etc., it is widely used in showing
Show, decorate, dress ornament, the fields such as anti-fake.Current existing luminescent fibre mainly include coloured fibre, fluorescent fiber, chameleon fibre,
Luminous fiber etc., wherein fluorescent fiber is presented particular color, is looked steadily because it is under special light (such as ultraviolet light) irradiation condition
Mesh is the big focus on research direction for researching and developing luminescent fibre.
Fluorescent fiber basis material currently on the market mostly uses chemical fibre, and main manufacturing method has melting to spin
Silk, solution-polymerized SBR, decoration method, chemic modified method, high-speed punching striking etc..The wherein manufacturing method of melt spinning, solution-polymerized SBR
It is in the fabrication process luminescent substance and polypropylene (PP), polyvinyl alcohol (PVA), terylene (PET), polymethyl methacrylate
(PMMA) etc. mixed with polymers spinning is made.And decoration method, chemic modified method be it is simple by fluorescent material directly in chemistry
Fiber surface coating.Although these types can prepare luminescent fibre, the luminescent fibre of these types of method manufacture all has one
Fixed disadvantage, the disadvantage that luminescent substance is easy to be destroyed, manufacturing process is complicated, equipment requirement is high, unfriendly to environment etc..And
And although the luminescent fibre manufactured has certain characteristics of luminescence, but be highly prone to the influence of external condition, and such as: it is illumination, molten
Agent, soda acid etc., make it lose luminosity, to no longer have the function of shining.High Speed Airflow Impact is even more also in reality
It tests the stage, does not there is mature technology at present.In general different methods to the requirement emphasis of production technology and luminescent substance not
Together, if method choice is improper, the mechanical performance of the luminescent fibre of preparation is seriously affected, and easily under the influence of external condition
Luminescent properties are poor or even disappear.Therefore, luminescent fibre selects method appropriate most important during the preparation process.
In consideration of it, special propose the application.
Summary of the invention
The present invention provides a kind of luminescent fibres, and can at least improve existing luminescent fibre influences vulnerable to external condition
And the problem of causing luminescent properties to be lost.
The present invention also provides a kind of preparation methods of luminescent fibre, and the stable luminescent fibre of performance can be made.
The present invention is implemented as follows:
A kind of luminescent fibre, including doughnut and the luminescent substance being carried in the doughnut.
A kind of preparation method of luminescent fibre, comprising: luminescent substance is carried in doughnut.
Luminescent fibre can be applied to prepare anti-fake product or fluorescent product.
The beneficial effects of the present invention are: the luminescent fibre that the present invention obtains by above-mentioned design, since luminescent substance being born
It is loaded in doughnut, avoids luminescent substance and be directly exposed to fiber surface, even if so that luminescent substance is chronically at stimulation
It is also not easily to fall off under the environment (washing, illumination, solvent, acid or alkali environment) of property, therefore the performance of luminescent fibre provided by the invention
Stablize, the product fluorescence property as made from the luminescent fibre is lasting.
The preparation method for the luminescent fibre that the present invention obtains by above-mentioned design, this method is simple, easy to operate.It can be made
The good luminescent fibre of stability.
When luminescent fibre provided by the invention is applied to prepare anti-fake product and fluorescent product, anti-fake product obtained has
Long-acting anti-counterfeit capability.When applied in fluorescent product, keep fluorescent product stability good, there is longer service life.
Detailed description of the invention
It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention
Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as
It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the SEM figure of luminescent fibre made from the embodiment of the present invention 1；
Fig. 2 is the fluorescence micrograph of luminescent fibre made from 1-3 of the embodiment of the present invention；
Fig. 3 is fluorescence spectra of the different luminescent fibres under the exciting light of 375nm；
Fig. 4 is the photo before and after the ultraviolet light irradiation of 375nm of luminescent fibre made from the embodiment of the present invention 1；
Fig. 5 is photo of the various products before and after the ultraviolet light irradiation of 375nm in experimental example 5；
Fig. 6 is the photo and fluorescence spectra of experiment front and back luminescent fibre in experimental example 6；
Fig. 7 is the luminous power and fluorescence spectra that sweat impregnates different time luminescent fibre in experimental example 7.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
A kind of luminescent fibre and preparation method thereof is provided to the embodiment of the present invention below to be specifically described.
A kind of luminescent fibre provided by the invention, including doughnut and the shiner being carried in the doughnut
Matter.
Luminescent substance is carried in doughnut, luminescent substance is avoided and is directly exposed to fiber surface, so that shining
Substance is not easily to fall off being chronically under irritating environment (washing, illumination, solvent, acid or alkali environment), therefore of the invention
The performance of the luminescent fibre of offer is stablized.
In the preferred embodiment of the present invention, luminescent substance growth in situ is in doughnut.In situ synthesis conduct
A kind of novel method for preparing composite material, have a characteristic that (1) binding strength is good: under given conditions, functive is in base
Organic centre and as " core " is formed on body, on matrix " crystallization ", growth naturally in situ.Due to being different from common physics
In conjunction with, it can be achieved that both functive and matrix perfect combination.(2) properties of product are excellent: growth in situ obtains composite material
It can stablize, and interface is pollution-free, obtains that functive particle is tiny, performance is stablized, and avoids matrix and function compatability is bad
The problem of, enhance the associativity between functive and matrix.Product multifunction: composite material can combine matrix and functive
The two advantage, is effectively improved the shortcomings that basis material has a single function, and realizes the multifunction of basis material.
In the preferred embodiment of the present invention, luminescent substance is that perovskite is nanocrystalline.Perovskite is nanocrystalline with following
Advantage: adjustable in 1. launch wavelength visible-ranges.2. having wider excitation spectrum and relatively narrow emission spectra, excellent without hangover etc.
Point, will be highly advantageous to its application in terms of colour developing.3. good light stability, anti-light bleachability is strong.So-called photobleaching, refers in light
Irradiation under the fluorescence intensity that is ejected of fluorescent material the phenomenon that gradually weakening or even disappear as time goes by.Light is stablized
Property be the application of most of fluorescent materials important indicator.4. biggish Stokes shift, can be to avoid emission spectrum and excitation
The overlapping of spectrum is conducive to the detection of fluorescence spectrum signal.5. quantum yield is high, all band is controllable.
Specifically, perovskite is nanocrystalline is made of monovalent cation, bivalent cation and univalent anion, the monovalence
The ratio between molal quantity of cationic, the described bivalent cation and the univalent anion is 1:1:3 or 4:1:6, the monovalence sun
Ion includes at least one of the cation containing amine groups, the cation containing amidine class group and cesium ion, the divalent
Cation includes at least one of lead ion and tin ion, and the univalent anion is at least one of halide ion.
Signified perovskite refers to the perovskite of broad sense in the present invention, is not the calcium titanyl of narrow sense being made of calcium titanate
The minerals of object.When the ratio between monovalent cation, the bivalent cation and molal quantity of the univalent anion in perovskite
It is three-dimensional perovskite for 1:1:3, and the ratio between monovalent cation, the bivalent cation and molal quantity of the univalent anion
Referred to as zero dimension perovskite when for 4:1:6, such as: Cs4PbBr6。
In the preferred embodiment of the present invention, doughnut wall thickness is 0.6-1.2 μm.Doughnut under this range was both
The toughness that can have guaranteed has preferable translucency again.It is highly preferred that the diameter of doughnut is 20 μm -28 μm, this diameter
Range weaves clothes or luminous sign as spinning convenient for luminescent fibre obtained.Specifically, doughnut can be plant
Fibres, animal origin or synthetic fibers.
A kind of preparation method of luminescent fibre provided by the invention, including luminescent substance is carried in doughnut.
Preferably, preparation method includes: to make luminescent substance growth in situ in doughnut.Luminescent substance growth in situ in
In doughnut luminescent substance is more firmly carried in doughnut, so that luminescent fibre stability obtained is good.
Specifically, luminescent substance is nanocrystalline for perovskite, the preparation method comprises the following steps:
Perovskite precursor solution is prepared first: monovalent cation salt and divalent cation salt being dissolved in solvent and obtained
Perovskite precursor solution.The monovalent cation salt includes at least one of halogeno-amine, halogenation amidine and caesium halide, the divalent sun from
Alite includes at least one of lead halide and tin halides.Preferably, the molar ratio of monovalent cation salt and divalent cation salt is
1:1, avoid finally dry after perovskite it is nanocrystalline in have have neither part nor lot in be formed the nanocrystalline monovalent cation salt of perovskite or and
Bivalent cation salt impurity.Preferably, the sum of monovalent cation salt and the amount of divalent cation salt in perovskite precursor solution
It is 0.04-0.12mmol:1mL to dry the obtained nanocrystalline life of perovskite in proof load to doughnut afterwards with the ratio between solvent
Long uniform, photism is good.Preferably, the solvent selection of perovskite precursor solution is to above-mentioned several salt solute effects preferable two
At least one of methyl sulfoxide and N,N-dimethylformamide.
It preferably, further include that surfactant is added thereto and is uniformly mixed in when preparing perovskite precursor solution,
Surfactant is that monovalent cation salt and bivalent cation reactant salt generate perovskite structure and provide coordination in the process so that anti-
Perovskite structure is stablized during answering, and then guarantees the nanocrystalline fluorescence quantum yield with higher of final perovskite obtained.
Preferably, surfactant volume is than the oleic acid and oleyl amine for 0.5-0.7:0.2-0.4.It is highly preferred that avoid crystalchecked
When agent waste can crystal stabilizer play one's part to the full to prepare perovskite precursor solution again, oleic acid and the monovalence sun from
The amount ratio of son is 0.5-1ml:0.4-0.6mmol.Oleyl amine generates oleyl amine cation in the reaction can form hydrogen bond with halogen,
Oleic acid generates oleic acid anion and caesium, lead ion coordination.Charge balance is kept, the structure of perovskite is stablized.When oleic acid and oleyl amine
The present invention claims in the range of when, the good perovskite of available shape characteristic is nanocrystalline.
Then doughnut is immersed in perovskite precursor solution, to the doughnut and the perovskite forerunner
System where liquid solution vacuumizes, and enters the perovskite precursor solution in the doughnut.Specifically:
The doughnut handled well is submerged in perovskite precursor solution, by perovskite precursor solution and hollow fibre
It ties up while being placed in vacuum evacuation device, then device is vacuumized.Being evacuated to system pressure for the first time is 0.07-0.09MPa,
2-5min is kept, is then evacuated to system pressure for the second time to 1~4h of 50Pa or less holding；Preferably, to make perovskite
Precursor solution is 10~15pa more rapidly and well into system pressure in doughnut, is evacuated to for the second time.Due to certain
A little doughnut one end have one section be it is curved, one end is closed, in order to enable perovskite precursor solution can be as early as possible
Into inside hollow fibre, therefore, it is necessary to cut off crooked end and closing end, crooked end about subtracts 0.5cm.Closed end
Portion about cuts off 0.3cm.Above-mentioned " handling well " doughnut refers to the doughnut that both ends are handled well.
Since doughnut mostly has hydrophobicity, is directly soaked in perovskite precursor solution, perovskite presoma
Solution is not easily accessed in doughnut, or the amount entered in doughnut is limited, and leads to luminescent fibre photism obtained
It can be slightly worse.Therefore select the mode vacuumized that precursor solution is made to enter doughnut in the application preferred embodiment
It is interior.
And why by the way of vacuumizing twice primarily to prevent doughnut from reuniting, cause load not
After uniformly happening.It is smaller that degree is vacuumized for the first time, is kept for a period of time when reaching required pressure, can extracted out hollow
Fibrous inside, which divides air and doughnut can also be effectively prevent all to focus on perovskite precursor solution surface under negative pressure, to be made
Reunite at doughnut, occurs so that perovskite precursor solution loads non-uniform phenomenon.It vacuumizes for the second time completely
Extract the air in doughnut out.After discharging vacuum, precursor solution is even into inside hollow fibre under the influence of air pressure.
Doughnut is directly submerged to perovskite forerunner it is noted that can be in other embodiments of the present invention
It is impregnated for a long time in liquid solution, luminescent fibre can also be made, but which preparation efficiency is low, luminescent fibre obtained shines
Property is poor.
Vacuum enters perovskite precursor solution in doughnut.After vacuumizing, taking out load has
The doughnut of perovskite precursor solution, will be hollow after vacuumizing to prevent solution from flowing out from the end of doughnut
The end bending of fiber is taken out from vaccum supply system to drying unit upwards, and end bending can prevent perovskite forerunner upwards
Liquid solution is flowed out from the end of doughnut.
Loading has the doughnut of perovskite precursor solution to be dried to solvent in drying unit volatilizees completely, after drying
It is nanocrystalline that perovskite precursor solution is converted into perovskite, and drying terminal is subject to it is observed that color of object, such as prepares green
Color luminescent fibre, then be dried to and be able to observe that green.Preferably, it can guarantee and do not break when drying temperature is 40~120 DEG C
Bad crystal structure, and produce crystal.It is highly preferred that drying temperature is 50~70 DEG C best, when drying temperature within this range
When, drying time is that 11~12h can guarantee that drying generates crystal completely.
It is existing prepare perovskite during, the preparation method used be into precursor solution be added toluene to be precipitated
The perovskite generated is recrystallized, and the mode of non-selected re crystallization from toluene prepares perovskite in the application, and it is selected at baking
Making in perovskite growth in situ to doughnut during dry, whole preparation process is participated in without other poor solvents (toluene),
Therefore protective effect is played to environment to a certain extent.
Luminescent fibre crude product is obtained after drying.It is nanocrystalline that the surface of luminescent fibre crude product may be also loaded perovskite.Cause
This, further includes successively rinsing luminescent fibre crude product to surface noresidue through toluene and methanol after drying.Then it does at room temperature
It is dry to get product.
Luminescent fibre provided by the invention can be applied to prepare anti-fake product or fluorescent product.Due to the luminescent fibre
Photism is good, and stability is good, therefore application has the anti-fake beautiful identifiability of the luminescent fibre strong, even if in extraneous irritation ring
Anti-counterfeiting performance is also not easy to lose under border, and applying has the fluorescence of the fluorescent product of the luminescent fibre good, long service life.
Specifically, when anti-fake product is anti-counterfeiting paper, the preparation method of anti-counterfeiting paper includes:
The luminescent fibre for being arranged as identification pattern is laid on one layer of paper pulp, tile one layer of paper pulp again on luminescent fibre
Obtain anti-fake product first product；Anti-fake product first product is dried, anti-counterfeiting paper is made.The anti-counterfeiting paper can be shown under ultraviolet lighting
Luminescent fibre arranges the identification pattern to be formed.
Preferably, if the length of luminescent fibre is inadequate, more luminescent fibres can be bonded as after long fibre, by long fibre
Identification pattern is arranged as to tile onto paper pulp again.The bonding agent that bonding luminescent fibre is used is polymethyl methacrylate
(PMMA)。
Long fibre obtained is also used as litzendraht wire other than it can be used to manufacture anti-counterfeiting paper, the production woven
Product have fluorescent effect.
When fluorescent product is fluorescent film, the preparation method of fluorescent film includes by luminescent fibre, polymethyl methacrylate
And organic solvent is uniformly mixed and obtains mixed liquor；Mixed liquor is tiled one layer and obtains fluorescent film in drying on plate.
Specifically: the organic solvent used in the embodiment of the present application is methylene chloride.To make tunnelluminescence obtained
Uniformly, luminescent fibre is cut into the staple fiber of the left and right 3mm long first.
Then, polymethyl methacrylate is dissolved in methylene chloride and obtains polymethyl methacrylate solution, it will be several
Staple fiber and polymethyl methacrylate solution are mixed evenly to obtain mixed liquor.Or the luminous fibre that will can also first cut short
Dimension is scattered in methylene chloride, and then into methylene chloride, dissolution polymethacrylamide is uniformly mixed again obtains mixed liquor.
Finally, mixed liquor is tiled one layer in glass dish, dry, so that methylene chloride evaporates, is shone at room temperature
Tunica fibrosa.
Fluorescent film obtained can be used for making fluorescence labelling, and the fluorescence property of obtained fluorescence labelling is stablized.
A kind of luminescent fibre provided by the invention and preparation method thereof is specifically described below in conjunction with specific embodiment.
Embodiment 1
The preparation method of luminescent fibre provided in this embodiment, comprising:
Step 1: by 0.4mmol PbBr2It is dissolved in 10mL n,N-Dimethylformamide with 0.4mmol CsBr, so
1mL oleic acid and 0.5mL oleyl amine is added thereto afterwards, dissolution standing obtains precursor solution after stirring 50min；
Be totally submerged step 2: the doughnut handled well is placed in precursor solution, the doughnut of selection it is straight
Diameter is 20 μm, and wall thickness is 0.6 μm；
Step 3: mixed solution is placed 3min under 0.08MPa vacuum condition, after continue to increase pressure and keep to 13Pa
4h；
Step 4: take out mixed liquor in doughnut, both ends be bent upwards it is angled so that precursor solution not
It must flow out.11h is placed at a temperature of 60 DEG C, solvent in doughnut chamber is volatilized complete；
Step 5: fiber successively rinses fiber outer wall using toluene and methanol solution after taking out, the calcium that outer wall generates is removed
Titanium ore is nanocrystalline, dries at room temperature, and luminescent fibre is made, and gained fiber issues the hair of green immediately under the irradiation of ultraviolet light
Light.The nanocrystalline structural formula of the perovskite of generation are as follows: CsPbBr3。
Embodiment 2
The preparation method of luminescent fibre provided in this embodiment, comprising:
Step 1: by 0.6mmol PbI2It is dissolved in 10mL dimethyl sulfoxide with 0.6mmol CsBr and is then added
0.6mL oleic acid and 0.3mL oleyl amine stand after stirring 50min dissolution and obtain precursor solution；
Be totally submerged step 2: the doughnut handled well is placed in above-mentioned mixed liquor, the doughnut of selection it is straight
Diameter is 28 μm, and wall thickness is 1.2 μm；
Step 3: precursor solution is placed 3min under 0.08MPa vacuum condition, after continue to increase pressure and protect to 13Pa
Hold 4h；
Step 4: taking out the doughnut in mixed liquor, both ends are bent upwards angled.It is placed at a temperature of 60 DEG C
11h volatilizees solvent in doughnut chamber complete；
Step 5: fiber successively rinses fiber outer wall using toluene and methanol solution after taking out, the calcium that outer wall generates is removed
Titanium ore is nanocrystalline, dries at room temperature, and luminescent fibre is made, and gained fiber issues red hair immediately under the irradiation of ultraviolet light
Light.The nanocrystalline middle monovalent cation of the perovskite of generation is cesium ion, bivalent cation is lead ion, univalent anion be iodine from
Son and bromide ion, monovalent cation: bivalent cation: the molar ratio of univalent anion is 1:1:3.
Embodiment 3
The preparation method of luminescent fibre provided in this embodiment, comprising:
Step 1: by 0.6mmol PbBr2It is dissolved in 10mL dimethyl sulfoxide with 0.6mmol CsCl, is then added
0.6mL oleic acid and 0.3mL oleyl amine stand after stirring 50min dissolution and obtain precursor solution；
It is totally submerged step 2: the doughnut handled well is placed in above-mentioned precursor solution, the doughnut of selection
Diameter be 25 μm, wall thickness be 1 μm；
Step 3: precursor solution is placed 3min under 0.08MPa vacuum condition, after continue to increase pressure and protect to 13Pa
Hold 4h；
Step 4: taking out the doughnut in mixed liquor, both ends are bent upwards angled.It is placed at a temperature of 60 DEG C
11h volatilizees solvent in doughnut chamber complete；
Step 5: fiber successively rinses fiber outer wall using toluene and methanol solution after taking out, the calcium that outer wall generates is removed
Titanium ore is nanocrystalline, dries at room temperature, and luminescent fibre is made, and gained fiber issues the hair of blue immediately under the irradiation of ultraviolet light
Light.The nanocrystalline middle monovalent cation of the perovskite of the nanocrystalline generation of the perovskite of generation is cesium ion, bivalent cation be lead from
Son, univalent anion are chloride ion and bromide ion, and monovalent cation: bivalent cation: the molar ratio of univalent anion is 1:1:
3。
Embodiment 4
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only, selects
Monovalent cation salt be CH3NH3I, divalent cation salt PbI2, dosage is 0.2mmol, is dissolved in 10ml N, N- diformazan
In the solvent of base formamide.The dosage of oleic acid is 0.5ml, and the dosage of oleyl amine is 0.2ml.Being evacuated to system pressure for the first time is
0.07MPa keeps 5min, and being evacuated to system pressure for the second time is 15Pa, keeps 3h.Drying temperature is set as 40 DEG C, keeps
12h.The nanocrystalline middle monovalent cation of the perovskite of generation is CH3NH3 +, bivalent cation be lead ion, univalent anion is iodine
Ion and bromide ion, monovalent cation: bivalent cation: the molar ratio of univalent anion is 1:1:3.
Embodiment 5
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only, selects
Monovalent cation salt be CH3NH3I, divalent cation salt SnI2, solvent is 10ml n,N-Dimethylformamide.Oleic acid
Dosage is 0.5ml, and the dosage of oleyl amine is 0.2ml.Being evacuated to system pressure for the first time is 0.07MPa, keeps 5min, for the second time
Being evacuated to system pressure is 15Pa, keeps 3h.Drying temperature is set as 40 DEG C, keeps 12h.During the perovskite of generation is nanocrystalline
Monovalent cation is CH3NH3 +, bivalent cation be tin ion, univalent anion is iodide ion, monovalent cation: divalent sun from
Son: the molar ratio of univalent anion is 1:1:3.
Embodiment 6
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only, selects
Monovalent cation salt be CH (NH2)2I, divalent cation salt PbI2, solvent is 10ml n,N-Dimethylformamide.Oleic acid
Dosage be 0.5ml, the dosage of oleyl amine is 0.2ml.For the first time be evacuated to system pressure be 0.07MPa, keep 5min, second
The secondary system pressure that is evacuated to is 15Pa, keeps 3h.Drying temperature is set as 40 DEG C, keeps 12h.The perovskite of generation is nanocrystalline
Middle monovalent cation is CH (NH2)2 +, bivalent cation be lead ion, univalent anion is iodide ion, monovalent cation: divalent
Cation: the molar ratio of univalent anion is 1:1:3.
Embodiment 7
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only, oleic acid
Dosage be 0.7ml, the dosage of oleyl amine is 0.2ml.For the first time be evacuated to system pressure be 0.08MPa, keep 3min, second
The secondary system pressure that is evacuated to is 50Pa, keeps 4h.Drying temperature is set as 120 DEG C, keeps 11h.
Embodiment 8
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only.Oleic acid
Dosage be 0.7ml, the dosage of oleyl amine is 0.4ml.For the first time be evacuated to system pressure be 0.09MPa, keep 2min, second
The secondary system pressure that is evacuated to is 10Pa, keeps 1h.Drying temperature is set as 50 DEG C, keeps 12h.
Embodiment 9
The preparation method of luminescent fibre provided in this embodiment is substantially same as Example 3, the difference is that only, oleic acid
Dosage be 0.5ml, the dosage of oleyl amine is 0.4ml.For the first time be evacuated to system pressure be 0.08MPa, keep 3min, second
The secondary system pressure that is evacuated to is 40Pa, keeps 4h.Drying temperature is set as 70 DEG C, keeps 11h.
Embodiment 10
The preparation method of luminescent fibre provided in this embodiment, comprising:
Step 1: by 0.6mmol PbBr2It is dissolved in 10mL n,N-Dimethylformamide with 0.6mmol CsBr, so
0.6mL oleic acid and 0.3mL oleyl amine is added thereto afterwards, standing obtains precursor solution after stirring 50min；
Be totally submerged step 2: the doughnut handled well is placed in precursor solution, the doughnut of selection it is straight
Diameter is 20 μm, and wall thickness is 0.6 μm；
Step 3: mixed solution is placed 3min under 0.08MPa vacuum condition, after continue to increase pressure and keep to 13Pa
4h；
Step 4: take out mixed liquor in doughnut, both ends be bent upwards it is angled so that precursor solution not
It must flow out.11h is placed at a temperature of 60 DEG C, solvent in doughnut chamber is volatilized complete；
Step 5: fiber successively rinses fiber outer wall using toluene and methanol solution after taking out, the calcium that outer wall generates is removed
Titanium ore is nanocrystalline, dries at room temperature, and luminescent fibre is made, and gained fiber issues the hair of green immediately under the irradiation of ultraviolet light
Light.The nanocrystalline structural formula of the perovskite of generation are as follows: Cs4PbBr6。
Embodiment 11
Present embodiments provide a kind of preparation method of fluorescent film:
0.64mg luminescent fibre made from embodiment 1 is cut into the staple fiber that length is 3mm, disperses 2ml for staple fiber
The first mixed liquor is obtained in methylene chloride, the second mixed liquor is obtained after 0.05gPMMA dissolution is added into the first mixed liquor, by the
Two mixed liquors tile one layer in glass dish, are dried to obtain fluorescent film at room temperature.
Embodiment 12
Present embodiments provide a kind of preparation method of anti-counterfeiting paper:
It is bonded together luminescent fibre made from embodiment 1 to obtain long fibre using PMMA, long fibre is arranged as marking
Know pattern to be laid on one layer of paper pulp, the one layer of paper pulp that then tiles again on identification pattern obtains anti-counterfeiting paper first product.To finally it prevent
Pseudo- paper first product dries to obtain anti-fake paper product.
Experimental example 1
Luminescent fibre made from embodiment 1 is shot into pattern under scanning electron microscope, it is as shown in Figure 1 to obtain SEM figure.
It can be seen from figure 1, luminescent fibre surface is uniform, does not have loaded nano crystal body.And have one in hollow fiber conduit
The layer nanocrystalline generation of perovskite.
Experimental example 2
The luminescent fibre fluorescent microscopy images (exciting light 380nm) that shooting embodiment 1-3 is obtained, hence it is evident that it can be seen that
The luminescent fibre of different emission, and it is uniform to shine.It can be seen that the outer wall light in fiber from the fluorescence microscope of light field
It is sliding, it is nanocrystalline without perovskite, it is simply present in the inner wall of fiber.A, d are that green fluorescence made from embodiment 1 is fine in Fig. 2
It ties up, b, e are red fluorescence fiber made from embodiment 2 in Fig. 2, and c, f are blue-fluorescence fiber made from embodiment 3 in Fig. 2.
Experimental example 3
Fig. 3 is under the exciting light of 375nm, the fluorescence spectra of three kinds of luminescent fibres (blue, green, red).It will be sent out made from Fig. 1
Fiber optics is placed under 375nm ultraviolet lamp and observes, it can be seen that it is as shown in Figure 4 that luminescent fibre issues strong fluorescence.
Experimental example 4
Display mark is made in fluorescent film made from embodiment 9: the pattern sheared in advance being laid on fluorescent film and is obtained
Display mark.Obtained display mark is irradiated in the UV lamp, the phosphor pattern of sending is as shown in Figure 5.Left side in Fig. 5
One group picture is the photo before and after the display mark ultraviolet light of school badge pattern.
Luminescent fibre made from embodiment 2 is bonded together using PMMA (0.05g/ml) solution, long hair optical fiber is made
Tie up line；The enterprising assassination of substrate by long luminescent fibre line in cross embroidery is embroidered into pattern；Under ultraviolet light irradiation, phosphor pattern is issued
As shown in Figure 5.A group picture among Fig. 5 is the photo before and after cross-stitch embroidery ultraviolet light.
The anti-counterfeiting paper of the pattern of LZU letter is made using the method that embodiment 10 improves.In the UV lamp by the anti-counterfeiting paper
Irradiation can show that fluorescence is as shown in Figure 5.A group picture on right side is the photo before and after anti-counterfeiting paper ultraviolet light in Fig. 5.
Experimental example 5
Luminescent fibre made from embodiment 1 is divided into two parts, shooting rinses front and back certainly after the flushing of second alcohol and water respectively
Under right light and the picture in the case where ultraviolet lamp takes, and fluorescence spectrum before and after flushing is measured, as shown in Figure 6.
In Fig. 6, a, f are initial luminescent fibre photo.C, h is photo in the UV lamp.B, g is respectively second alcohol and water
Rinse later photo.D, i is photo in the UV lamp.E, j is the fluorescence spectrum after second alcohol and water rinses respectively.
From in fluorescence spectrum, it can be seen that fluorescence property decreased significantly after ethyl alcohol rinses, but according to the photo of shooting
From the point of view of, without significant difference before fluorescence property and flushing.From in fluorescence spectrum, it can be seen that after water rinses fluorescence property slightly have under
Drop, but according to the photo of shooting from the point of view of, fluorescence property and rinse before without significant difference.And under normal conditions, existing luminous fibre
Dimension is after water and ethyl alcohol rinse, and especially after ethyl alcohol rinses, fluorescence property has apparent macroscopic be greatly reduced
Situation.Then in this application, luminescent fibre fluorescence property after water and ethyl alcohol rinse is almost unchanged, and thus, it is possible to illustrate this Shen
Please luminescent fibre obtained stability it is good.
Luminescent fibre luminescent substance made from the application is not easily to fall off, and stability is good, and product obtained is durable.
Experimental example 6
Synthesis of artificial sweat, artificial sweat's synthetic method: under stiring, by 0.5g niacin (C6H5NO2), 0.16g NaCl
With 0.06g urea (CH4N2O it) is dissolved in 100mL deionized water (36 DEG C), pH value is adjusted to 5.4.It will be made from embodiment 1
Luminescent fibre is immersed directly in the fluorescence pond containing sweat, is placed in air.Separated in time detects luminescent fibre
Fluorescence intensity is recorded into a figure of Fig. 7.Draw the fluorescence spectrum that soaking time is respectively 0,6,28,50 hour luminescent fibre
Curve is into the b figure of Fig. 7.
Fig. 7 shows, in a after continuous immerse artificial sweat 100 minutes, the luminous intensity of fiber only slightly decline (~
10%).The fluorescence spectra of figure b shows that fiber is still luminous even across after 50 hours.Thus it can also illustrate this hair
The stability of luminescent fibre made from bright embodiment is good.
In conclusion luminescent fibre provided by the present application avoids hair since luminescent substance to be carried in doughnut
Stimulative substance is directly exposed to fiber surface, even if so that luminescent substance be chronically at irritating environment (washing, illumination, solvent,
Acid or alkali environment) under it is also not easily to fall off, therefore the performance of luminescent fibre provided by the invention stablize, as made from the luminescent fibre produce
Product fluorescence property is lasting.
When luminescent fibre provided by the invention is applied in anti-fake product and fluorescent product, anti-fake product has long-acting anti-fake
Ability.When applied in fluorescent product, keep fluorescent product stability good, there is longer service life.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of luminescent fibre, which is characterized in that including doughnut and the luminescent substance being carried in the doughnut.
2. luminescent fibre according to claim 1, which is characterized in that the luminescent substance is that perovskite is nanocrystalline；
Preferably, the perovskite is nanocrystalline is made of monovalent cation, bivalent cation and univalent anion, the monovalence
The ratio between molal quantity of cationic, the described bivalent cation and the univalent anion is 1:1:3 or 4:1:6, the monovalence sun
Ion includes at least one of the cation containing amine groups, the cation containing amidine class group and cesium ion, the divalent
Cation includes at least one of lead ion and tin ion, and the univalent anion is at least one of halide ion；
It is highly preferred that the halide ion includes Cl﹣、Br﹣And I﹣At least one of；
Preferably, the luminescent substance growth in situ is in the doughnut.
3. luminescent fibre according to claim 1, which is characterized in that the doughnut wall thickness is 0.6-1.2 μm；
Preferably, the degree of hollowness of the doughnut is 80%-90%；
Preferably, the diameter of the doughnut is 20 μm -28 μm；
Preferably, the doughnut is plant fiber, animal origin or synthetic fibers.
4. a kind of preparation method of luminescent fibre characterized by comprising luminescent substance to be carried in doughnut.
5. the preparation method of luminescent fibre according to claim 4, which is characterized in that
Preparation method includes: to make luminescent substance growth in situ in the doughnut；
Preferably, the luminescent substance is that perovskite is nanocrystalline, makes luminescent substance growth in situ in being in the doughnut:
The doughnut is immersed in perovskite precursor solution, it is molten to the doughnut and the perovskite presoma
System where liquid discharges after vacuumizing, and enters the perovskite precursor solution in the doughnut；
The doughnut that load has precursor solution is dried to solvent to volatilize completely；
Preferably, system where the doughnut and the perovskite precursor solution is vacuumized, before making the perovskite
Drive liquid solution enters in the doughnut: being evacuated to system pressure for the first time is 0.07-0.09MPa, keeps 2-5min,
Then it is evacuated to system pressure for the second time to 1~4h of 50Pa or less holding；It is highly preferred that being evacuated to system pressure for the second time
For 10~15pa；
Preferably, the doughnut wall thickness is 0.6-1.2 μm；
Preferably, the diameter of the doughnut is 20 μm -28 μm；
Preferably, drying temperature is 40~120 DEG C, it is highly preferred that drying temperature is 50~70 DEG C, drying time is 11~12h；
Preferably, before the doughnut that load has precursor solution being dried further include: load is had the hollow of precursor solution
Fiber takes out from the system vacuumized, and taking-up process keeps load to have the end of the doughnut of precursor solution to be bent up
It is bent.
6. the preparation method of luminescent fibre according to claim 5, which is characterized in that perovskite precursor solution is by one
Valence cationic salts and divalent cation salt, which are dissolved in solvent, to be obtained, wherein the monovalent cation salt includes halogeno-amine, halogenation
At least one of amidine and caesium halide, the divalent cation salt include at least one of lead halide and tin halides；
Preferably, the halogen in the monovalent cation salt and the divalent cation salt is chlorine, bromine or iodine；
Preferably, the solvent is at least one of dimethyl sulfoxide and n,N-Dimethylformamide；
Preferably, the molar ratio of the monovalent cation salt and the divalent cation salt is 1:1；
Preferably, the sum of amount of monovalent cation salt described in the perovskite precursor solution and the divalent cation salt with
The ratio between described solvent is 0.04-0.12mmol:1mL；
It preferably, include surfactant in the perovskite precursor solution；It is highly preferred that the surfactant includes body
Product is than the oleic acid and oleyl amine for 0.5-0.7:0.2-0.4, it is highly preferred that preparing the oleic acid when perovskite precursor solution
Amount ratio with the monovalent cation is 0.5-1ml:0.4-0.6mmol.
7. the preparation method of luminescent fibre according to claim 5, which is characterized in that be dried to after solvent volatilizees completely and obtain
To after luminescent fibre crude product, further includes:
The luminescent fibre crude product is successively rinsed through toluene and methanol to surface noresidue, the fibre that shines then is dried to obtain
Dimension.
8. luminescent fibre as described in any one of claims 1-3 or such as the described in any item luminescent fibres of claim 4-7
Luminescent fibre made from preparation method is preparing anti-fake product or is preparing the application in fluorescent product.
9. application according to claim 8, which is characterized in that the anti-fake product is anti-counterfeiting paper, the system of the anti-counterfeiting paper
Preparation Method includes:
The luminescent fibre for being arranged as identification pattern is laid on one layer of paper pulp, is tiled again on the luminescent fibre one layer
Paper pulp obtains anti-counterfeiting paper first product；
The anti-counterfeiting paper first product is dried；
Preferably, before the luminescent fibre for being arranged as identification pattern being laid on one layer of paper pulp further include:
The luminescent fibre is bonded as luminescent fibre line, the luminescent fibre line is then arranged as the identification pattern；More
Preferably, use polymethyl methacrylate that the luminescent fibre is bonded as the luminescent fibre line.
10. application as claimed in claim 8, which is characterized in that the fluorescent product is fluorescent film, the preparation of the fluorescent film
Method includes:
The luminescent fibre, polymethyl methacrylate and organic solvent are uniformly mixed and obtain mixed liquor；
The mixed liquor is tiled one layer and obtains fluorescent film in drying on plate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957748A (en) * | 2021-10-28 | 2022-01-21 | 山东天和纸业有限公司 | Fiber and fluorescence anti-counterfeiting paper and preparation method thereof |
| WO2023078185A1 (en) * | 2021-11-02 | 2023-05-11 | 华为技术有限公司 | Colored fiber, colored fiber part, fiber reinforced composite material, structural part, and preparation method |
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