CN115894778B - Holographic polymer composite material, preparation method and application thereof - Google Patents
Holographic polymer composite material, preparation method and application thereof Download PDFInfo
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- CN115894778B CN115894778B CN202211549422.5A CN202211549422A CN115894778B CN 115894778 B CN115894778 B CN 115894778B CN 202211549422 A CN202211549422 A CN 202211549422A CN 115894778 B CN115894778 B CN 115894778B
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 125
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- 239000002105 nanoparticle Substances 0.000 claims abstract description 52
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 230000001427 coherent effect Effects 0.000 claims abstract description 32
- 238000003860 storage Methods 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000005191 phase separation Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 31
- -1 N-dimethylacrylamide Chemical compound 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 20
- 238000004020 luminiscence type Methods 0.000 claims description 19
- 230000001678 irradiating effect Effects 0.000 claims description 18
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 12
- 238000011417 postcuring Methods 0.000 claims description 11
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 claims description 10
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910021644 lanthanide ion Inorganic materials 0.000 claims description 9
- HHPCNRKYVYWYAU-UHFFFAOYSA-N 4-cyano-4'-pentylbiphenyl Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C#N)C=C1 HHPCNRKYVYWYAU-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 7
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 6
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 6
- 150000004775 coumarins Chemical class 0.000 claims description 6
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
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- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical class N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 claims description 4
- ZGOWXOZNUNZPAV-UHFFFAOYSA-N 4-(4-heptylphenyl)benzonitrile Chemical group C1=CC(CCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 ZGOWXOZNUNZPAV-UHFFFAOYSA-N 0.000 claims description 4
- GPGGNNIMKOVSAG-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzonitrile Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 GPGGNNIMKOVSAG-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- PJPLBHHDTUICNN-UHFFFAOYSA-N 4-(4-butylphenyl)benzonitrile Chemical group C1=CC(CCCC)=CC=C1C1=CC=C(C#N)C=C1 PJPLBHHDTUICNN-UHFFFAOYSA-N 0.000 claims description 3
- QXAMGWKESXGGNV-UHFFFAOYSA-N 7-(diethylamino)-1-benzopyran-2-one Chemical compound C1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 QXAMGWKESXGGNV-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- UVZUFUGNHDDLRQ-LLHZKFLPSA-N cholesteryl benzoate Chemical compound O([C@@H]1CC2=CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)C(=O)C1=CC=CC=C1 UVZUFUGNHDDLRQ-LLHZKFLPSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 3
- 229940065472 octyl acrylate Drugs 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
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- 229910052769 Ytterbium Inorganic materials 0.000 description 23
- 229910052775 Thulium Inorganic materials 0.000 description 16
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 12
- 229910052688 Gadolinium Inorganic materials 0.000 description 11
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- 238000005516 engineering process Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 235000001671 coumarin Nutrition 0.000 description 6
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 238000003384 imaging method Methods 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000005212 4-Cyano-4'-pentylbiphenyl Substances 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 2
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- KPQVQWUNELODQE-UHFFFAOYSA-N 4-(4-butoxyphenyl)benzonitrile Chemical group C1=CC(OCCCC)=CC=C1C1=CC=C(C#N)C=C1 KPQVQWUNELODQE-UHFFFAOYSA-N 0.000 description 1
- 239000005253 4-Cyano-4'-heptylbiphenyl Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
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- UWBXIFCTIZXXLS-UHFFFAOYSA-L disodium;2,3,4,5-tetrachloro-6-(2,4,5,7-tetraiodo-3-oxido-6-oxoxanthen-9-yl)benzoate Chemical class [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 UWBXIFCTIZXXLS-UHFFFAOYSA-L 0.000 description 1
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- Holo Graphy (AREA)
Abstract
The invention discloses a holographic polymer composite material for triple image storage, which is prepared by up-conversion nano particles, liquid crystal and photopolymerization monomers through coherent laser polymerization induced phase separation; the composite material specifically comprises 3-15 wt% of photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal and 30-74 wt% of photopolymerization monomer; the composition also comprises 0.1 to 5 percent of photoinitiator accounting for the total weight; in the same spatial position of the composite material, not only can a high-brightness holographic image and a color-changing image be presented under sunlight, but also an up-conversion luminous image can be presented under the excitation of a dot near infrared laser light source; the area of the up-conversion luminous image is 2-225 times of the spot area of the dot near infrared laser. The invention also discloses a corresponding preparation method and application. The invention can be used in the high-end anti-counterfeiting field, and solves the technical problems that single image anti-counterfeiting in the prior art is difficult to ensure safety, and up-conversion image is too small in size to be identified by naked eyes.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a holographic polymer/liquid crystal/up-conversion nanoparticle composite material with up-conversion luminescence and light response characteristics, a preparation method and application thereof.
Background
For a long time, counterfeit products seriously threaten the security of folk life, economy and national defense, so that the anti-counterfeiting has important significance for both countries and individuals. Holographic technology is an effective means of image storage. The basic principle of holographic technology is: two coherent lasers in space interfere to form a grating, and the amplitude and phase information of the coherent lasers are recorded simultaneously, so that three-dimensional (3D) information storage is realized. The holographic technology has the characteristics of higher process imitation difficulty, good visual effect of recorded images, remarkable mass recognition capability and the like, and plays an important role in the field of optical anti-counterfeiting. However, with the development of technology and the leakage of anti-counterfeiting technology, a single holographic anti-counterfeiting technology is difficult to meet the high-end anti-counterfeiting requirement.
Multiple optical anti-counterfeiting technologies are integrated, multiple images are displayed in the same space under different conditions, and the information capacity and the security level can be remarkably improved. However, how to realize multiple images in a single material that are distinguishable to the naked eye and do not cross-talk each other still faces a great challenge. The up-conversion nano particle is a nano particle which is excited by infrared light and has adjustable luminous color, can be mutually independent from the traditional photoluminescence image and holographic image, and provides a new thought for storing multiple information. However, the display of the up-converted image still needs to be performed by professional equipment, and a large up-converted image visible to naked eyes cannot be obtained. The up-conversion nano particles are introduced into the holographic material after being subjected to surface modification by the fluorescein isothiocyanate, and the holographic and up-conversion dual-image storage (ACS appl. Mater. Interfaces 2021,13,19159-19167) can be realized through energy transfer between the up-conversion nano particles and the fluorescein isothiocyanate, but the up-conversion nano particles are limited by small near infrared laser spots, the power after beam expansion is low, and only up-conversion luminous images with the diameter of 2 millimeters at maximum can be formed.
In summary, the current large-size up-conversion luminescence image still depends on point-by-point scanning and time-lapse photography for observation, consumes time and depends on equipment, and cannot realize naked eye observation.
Disclosure of Invention
Aiming at one or more of the defects or improvement demands of the prior art, the invention provides a holographic polymer composite material, a preparation method and application thereof, and the holographic polymer composite material has holographic images, color-changing images and up-conversion luminescent images, and solves the technical problems that the security is difficult to ensure by single image anti-counterfeiting and the up-conversion images are too small to be identified by naked eyes in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a holographic polymeric composite material for triple image storage,
the composite material is prepared by up-conversion nano particles, liquid crystal and photopolymerization monomers through coherent laser polymerization induced phase separation; in the same spatial position of the composite material, not only can a high-brightness holographic image and a color-changing image be presented under sunlight, but also an up-conversion luminous image can be presented under the excitation of a dot near infrared laser light source; the area of the up-conversion luminous image is 2-225 times of the spot area of the dot near infrared laser.
As a further improvement of the invention, the wavelength of the punctiform near-infrared laser light source is 808-1532 nm, and the spot diameter of the punctiform near-infrared laser is 0.2-0.4 cm; the up-conversion luminescence image has a diameter of 0.5-3 cm.
As a further improvement of the present invention, the composite material comprises: 3 to 15 weight percent of photochromic compound, 2 to 15 weight percent of up-conversion nano particles, 9 to 45 weight percent of liquid crystal and 30 to 74 weight percent of photopolymerization monomer; and further comprises 0.1-5% of photoinitiator based on the total weight.
As a further improvement of the invention, the up-conversion nanoparticle is a lanthanide ion doped N modified with a surface ligandaYF 4 ；
The lanthanide ion comprises Yb 3+ At the same time comprise Gd 3+ 、Er 3+ And Tm 3+ The Yb is one of 3+ 、Gd 3+ 、Er 3+ 、Tm 3+ The molar weight of the catalyst accounts for 10 to 80 percent, 0 to 15 percent and 0 to 10 percent of the total molar weight of the lanthanide ions respectively.
As a further improvement of the present invention, the photochromic compound comprises one or more of diarylethenes, spiropyrans, azobenzene, wherein the diarylethenes have the following structural formula:
wherein Ar is 1 、Ar 2 Each independently selected from any one of the following structural formulas I, II, III, IV, V and VI:
wherein the site marked as a radical attachment site is attached in formula A, B, C, D; and substituent R 1 、R 2 Each independently selected from hydrogen, methyl, ethyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or cyanostilbene derivatives;
the structural formula of the spiropyrans is as follows:
the structural formula of the azobenzene is as follows:
knot of the spiropyrans and azobenzeneIn the structural formula, substituent R 1 、R 2 Each independently selected from hydrogen, methyl, ethyl, n-pentyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or stilbene derivatives.
As a further improvement of the present invention, the liquid crystal is one or more of commercial P0616A, 4-n-butyl-4 '-cyanobiphenyl, 4-n-pentyl-4' -cyanobiphenyl, 4-n-heptyl-4 '-cyanobiphenyl, 4-n-octyloxy-4' -cyanobiphenyl, 4-n-pentyl-4 '-cyanobiphenyl, 4-4' -azobisite, cholesteryl benzoate, commercial JC-M-LC-TD.
As a further improvement of the present invention, the photopolymerizable monomers include monofunctional monomers and polyfunctional monomers;
the monofunctional monomer comprises one or more of N-vinyl pyrrolidone, acrylamide, methacrylamide, N-dimethylacrylamide, isobornyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethyl methacrylate and N-vinyl carbazole;
the multifunctional monomer includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, ethylene glycol dimethacrylate, and commercial hyperbranched monomers 6361-100.
As a further improvement of the present invention, the photoinitiator is an ultraviolet initiator or a visible photoinitiator;
the visible light initiator is a mixture of bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, 3' -carbonylbis (7-diethylaminocoumarin) and N-phenylglycine or a mixture of tetraiodotetrachlorofluorescein sodium salt and N-phenylglycine;
the ultraviolet initiator is a mixture of di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2-hydroxy-2-methyl-1-phenyl acetone.
According to a second aspect of the present invention, there is provided a method for preparing the holographic polymer composite material for triple image storage, comprising the steps of:
s1: uniformly mixing 3-15 wt% of photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal, 30-74 wt% of photopolymerization monomer and 0.1-5% of photoinitiator based on the total weight to obtain a composite material precursor;
s2: packaging the composite material precursor obtained in the step S1 in a liquid crystal box, and adopting coherent laser irradiation to polymerize the photopolymerization monomer to obtain a holographic material stored with a holographic image;
s3: irradiating the holographic material obtained in the step S2 by ultraviolet light through a mask plate to obtain a composite material which stores a holographic image, a color-changing image and an up-conversion image simultaneously; the mask plate is used for defining a color-changing image and an up-conversion luminescence image;
s4: and (3) performing post-curing on the composite material obtained in the step (S3) by adopting visible light or ultraviolet light, and fixing the obtained image.
Preferably, in step S1, the mixing method is as follows: magnetic stirring or ultrasonic treatment is carried out for 30-120 minutes at 20-90 ℃.
Preferably, in step S2, the coherent laser wavelength is 432-633 nm, and the coherent laser irradiation time is 30-180 seconds.
Preferably, in step S3, the wavelength of the ultraviolet light is 200-370 nm, the irradiation light intensity is 0.5-2 milliwatts/square centimeter, and the irradiation time is 5-15 minutes.
Preferably, in step S4, the post-curing time is 12-24 hours.
According to a third aspect of the invention there is provided the use of a holographic polymeric composite material for triple image storage as described in the field of optical security, optical information storage or display.
The invention provides a composite material storing dot near infrared laser excited up-conversion luminescent images which can be observed by naked eyes, a preparation method and application thereof, which overcomes the technical problems of integrated storage of multiple images and naked eye display of up-conversion images by redesigning and improving the composition and the preparation method of the composite material, and correspondingly obtains the composite material with holographic images, color-changing images and up-conversion luminescent images, thereby solving the technical problems that the security of single image anti-counterfeiting is difficult to ensure and the size of the up-conversion images is too small to be identified by naked eyes in the prior art.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
according to the invention, through the introduction of the up-conversion nano particles, the up-conversion luminescence is transmitted in the liquid crystal layer of the material by utilizing the phase separation structure and refractive index difference between the liquid crystal and the polymer and utilizing the optical waveguide effect, so that the 'point and surface' luminescence is realized; and through energy transfer between the photochromic molecules and the up-conversion nano particles, the imaging of up-conversion luminescence is realized, and the problems that the up-conversion luminescence imaging cannot be recognized by naked eyes, the size is small and the resolution is low are effectively solved (as shown in figure 1). The technical scheme can realize naked eye identification, high brightness and high contrast of the up-conversion image under near infrared light, and can ensure that the brightness of the holographic image is not affected. Independent coexistence of the holographic image, the color-changing image and the up-conversion image is realized, and storage of the triple images is realized.
The invention successfully combines holographic anti-counterfeiting with up-conversion anti-counterfeiting, displays holographic images and color-changing images under different conditions of the same spatial position to up-convert luminescent images, realizes organic unification of explicit anti-counterfeiting and implicit anti-counterfeiting, and effectively improves anti-counterfeiting capability.
The holographic polymer composite material for triple image storage provided by the invention not only has important application in the field of high-end optical anti-counterfeiting, but also can be applied to the fields of optical information storage, displays and the like.
Drawings
FIG. 1 is a schematic diagram of naked eye identification of an up-conversion image according to an embodiment of the present invention;
FIG. 2 is a holographic image reproduced from diffracted light in daylight according to example 5 of the present invention;
FIG. 3 is a color change image obtained in daylight according to example 5 of the present invention;
fig. 4 is an up-conversion luminescence image obtained under excitation of dot-like near infrared light according to example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a holographic polymer composite material for triple image storage and a preparation method thereof. The composite material has triple image functions, can observe holographic images and color-changing images under natural light, and can observe up-conversion luminescent images visible to naked eyes under near infrared laser.
The holographic polymer composite material is prepared by up-conversion nano particles, liquid crystal and photopolymerization monomers through coherent laser polymerization induced phase separation; the method comprises the steps of forming a uniform dispersion by a photopolymerizable monomer, a photoinitiator, liquid crystal and up-conversion nano particles, packaging the uniform dispersion in a transparent liquid crystal box, and finally irradiating the uniform dispersion under coherent laser to enable the photopolymerizable monomer to undergo free radical polymerization, so as to obtain the holographic material storing holographic images. Writing the color-changing image and the up-conversion luminescent image by ultraviolet light at the same space position of the holographic material storing the holographic image, and defining the shapes of the color-changing image and the up-conversion luminescent image by using a mask. And finally, obtaining the composite material simultaneously storing the triple image information.
The composite material can not only present high-brightness holographic images and color-changing images in the same space position, but also present up-conversion luminescent images under the excitation of dot near infrared laser light sources; the area of the up-conversion luminous image is 2-200 times of the spot area of the dot near infrared laser.
Wherein the wavelength of the punctiform near-infrared laser light source is 808-1532 nm, and the diameter of the punctiform near-infrared laser light spot is 0.2-0.4 cm; the up-conversion luminescence image has a diameter of 0.5-3 cm.
Specifically, the holographic polymer composite material comprises 3-15 wt% of photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal and 30-74 wt% of photopolymerization monomer; and further comprises 0.1-5% of photoinitiator based on the total weight.
Wherein the up-conversion nano-particles are surface ligand modified lanthanide ion doped NaYF 4 The method comprises the steps of carrying out a first treatment on the surface of the The lanthanide ion comprises Yb 3+ At the same time comprise Gd 3+ 、Er 3+ And Tm 3+ Yb of (a) and Yb 3+ 、Gd 3+ 、Er 3+ 、Tm 3+ The molar weight of the catalyst accounts for 10 to 80 percent, 0 to 15 percent and 0 to 10 percent of the total molar weight of the lanthanide ions respectively.
Further, the photochromic compound comprises one or more of diarylethenes, spiropyrans, azobenzene, wherein the diarylethenes have the following structural formula:
wherein Ar is 1 、Ar 2 Each independently selected from any one of the following structural formulas I, II, III, IV, V and VI:
wherein the site marked as a radical attachment site is attached in formula A, B, C, D; and substituent R 1 、R 2 Each independently selected from hydrogen, methyl, ethyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or cyanostilbene derivatives;
the structural formula of the spiropyrans is as follows:
the structural formula of the azobenzene is as follows:
in the structural formulas of the spiropyrans and the azobenzene, the substituent R 1 、R 2 Each independently selected from hydrogen, methyl, ethyl, n-pentyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or stilbene derivatives.
Further, the liquid crystal is one or more of commercial P0616A, 4-n-butyl-4 '-cyanobiphenyl, 4-n-amyl-4' -cyanobiphenyl, 4-n-heptyl-4 '-cyanobiphenyl, 4-n-octyloxy-4' -cyanobiphenyl, 4-n-amyl-4 '-cyanobiphenyl, 4-4' -azobisite, cholesteryl benzoate and commercial JC-M-LC-TD.
Further, the photopolymerizable monomer includes a mixture of a monofunctional monomer and a polyfunctional monomer, and the mass ratio of the monofunctional monomer to the polyfunctional monomer is preferably 3:1 to 1:2; wherein,
the monofunctional monomer comprises one or more of N-vinyl pyrrolidone, acrylamide, methacrylamide, N-dimethylacrylamide, isobornyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, ethyl 2-methacrylate and N-vinyl carbazole;
the multifunctional monomers include one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, ethylene glycol dimethacrylate, and commercial hyperbranched monomers 6361-100.
The specific mass fractions of the monofunctional monomer and the polyfunctional monomer depend on the molecular weight of the monomers and the number of carbon-carbon double bonds contained in the compound; the optimal mass fraction is such that the number of carbon-carbon double bonds of the monofunctional monomer is about the same as that of the polyfunctional monomer.
Further, the photoinitiator is a photoinitiator suitable for a coherent laser excited free radical polymerization reaction, and specifically comprises an ultraviolet light initiator or a visible light initiator; wherein,
the visible light initiator is a mixture of bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, 3' -carbonyl bis (7-diethylaminocoumarin) and N-phenylglycine or a mixture of tetraiodotetrachlorofluorescein sodium salt and N-phenylglycine; the ultraviolet initiator is a mixture of bis (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2-hydroxy-2-methyl-1-phenyl acetone.
The preparation method of the holographic polymer composite material for triple image storage comprises the following steps:
s1: uniformly mixing 3-15 wt% of photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal, 30-74 wt% of photopolymerization monomer and 0.1-5% of photoinitiator based on the total weight to obtain a composite material precursor;
in a preferred embodiment, the method for uniformly mixing the components comprises the following steps: magnetic stirring or ultrasonic treatment is carried out for 30-120 minutes at 20-90 ℃.
S2: packaging the composite material precursor obtained in the step S1 in a liquid crystal box, and adopting coherent laser irradiation to polymerize the photopolymerization monomer to obtain a holographic material stored with a holographic image;
in a preferred embodiment, the coherent laser wavelength is 432-633 nm, preferably 532 nm; the coherent laser irradiation time is 30-180 seconds.
The principle of holographic imaging is: one beam of laser generates two beams of homologous coherent light through a spectroscope, wherein one beam of laser irradiates an object to generate diffuse reflection light (abbreviated as object light), then interferes with the other beam of homologous laser (abbreviated as reference light) to form a grating, and simultaneously records the phase and amplitude information of the coherent light on a recording medium (precursor of a dual-image storage material) to realize 3D holographic information storage.
S3: irradiating the holographic material obtained in the step S2 by ultraviolet light through a mask plate to obtain a composite material which stores a holographic image, a color-changing image and an up-conversion image simultaneously;
in a preferred embodiment, the ultraviolet light has a wavelength of 200-370 nanometers, an illumination intensity of 0.5-2 milliwatts per square centimeter, and an illumination time of 5-15 minutes.
The mask is used for defining a color-changing image and an image of an up-conversion luminescent image, the mask is made of two materials, wherein one material allows ultraviolet light to pass through, such as soda glass, the other material does not allow ultraviolet light to pass through, such as metal, the mask is made of metal to form a required image, ultraviolet light cannot pass through the image area, other parts of the material are subjected to ultraviolet exposure, and photochromic molecules undergo conformational transition, so that a corresponding color-changing image and an up-conversion luminescent image can be formed on the material.
S4: and (3) post-curing the composite material obtained in the step (S3) by adopting visible light or ultraviolet light, and fixing the obtained image:
in a preferred embodiment, the post-cure time is 12-24 hours.
The holographic polymer/liquid crystal/up-conversion nanoparticle composite material provided by the invention has the characteristics of triple anti-counterfeiting and hidden anti-counterfeiting, has high image contrast and simple manufacture, and can be applied to the fields of optical anti-counterfeiting, optical information storage or display. When the composite material provided by the invention is used for triple anti-counterfeiting, a holographic image can be observed by diffraction under visible light, and a color-changing image can be observed by reflection; under the irradiation of near infrared light, the optical waveguide characteristic of the liquid crystal and the near infrared excitation visible light characteristic of the up-conversion nano particles can be utilized, so that the naked eye can observe an up-conversion luminous image which is determined by mask pattern images in the composite material in advance.
In addition, the holographic image, the color-changing image and the up-conversion luminescent image of the present invention may be the same or different; the holographic image can be a two-dimensional image or a three-dimensional image, but can be observed with naked eyes in sunlight.
The following are examples:
example 1
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 2 cm by being excited by a dot 980 nm laser light source with the diameter of 2 mm, and the area of the obtained images is 100 times of the area of light spots.
The composite material consists of 5wt% of photochromic molecular diaryl ethylene (structural formula A, ar 1 、Ar 2 Are all I, R 1 、R 2 All groups are benzene rings), 10wt% of up-conversion nanoparticles (which contain 60mol% Y 3+ 、30mol％Yb 3+ 、2mol％Er 3 + And 8mol% Gd 3+ ) 35wt% of liquid crystal 4-cyano-4' -pentylbiphenyl (5 CB), 0.4wt% of photoinitiator and 50wt% of photopolymerization monomer are obtained by phase separation induced by coherent laser polymerization.
Wherein the photoinitiator is a mixture of a visible light initiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine. The photo-polymerization monomer is a mixture of a monofunctional monomer ethyl acrylate and a polyfunctional monomer pentaerythritol triacrylate according to a mass ratio of 3:1.
The preparation method of the composite material in the embodiment is as follows:
firstly, diaryl ethylene molecules and up-conversion nano particles are added into a mixed solution of a photopolymerization monomer and 4-cyano-4 '-amyl biphenyl (5 CB) liquid crystal, and then a photoinitiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine are added into the mixed solution, and are subjected to ultrasonic dispersion for 60 minutes at 20 ℃ so that the photoinitiator, the diaryl ethylene molecules and the up-conversion nano particles are uniformly dispersed in the mixed solution of the monomer and the liquid crystal, and a composite material precursor is prepared.
And irradiating the composite material precursor for 30 seconds under 432-nanometer coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. And then, using a mask plate to irradiate for 10 minutes under 365 nanometers and ultraviolet light with the light intensity of 2 milliwatts per square centimeter, so as to obtain the composite material simultaneously storing the holographic image, the color-changing image and the up-conversion luminescent image. Finally, the obtained composite material is irradiated by visible light for 16 hours to carry out post-curing, so that the residual photopolymerization monomer is completely reacted, and the image is fixed.
Example 2
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 0.5 cm by being excited by a dot 975 nanometer laser light source with the diameter of 3 mm, and the area of the obtained images is about 3 times of the area of light spots.
The composite material consists of 5wt% of photochromic molecular diaryl ethylene (structural formula A, ar 1 、Ar 2 Are all I, R 1 、R 2 All groups are n-pentyl), 10wt% of up-conversion nanoparticles (containing 30mol% Gd 3+ 、50mol％Y 3+ 、2mol％Er 3+ And 18mol% Yb 3+ ) 35wt% of liquid crystal 4-cyano-4' -pentylbiphenyl (5 CB), 0.4% of photoinitiator and 50wt% of photopolymerization monomer are obtained by phase separation induced by coherent laser polymerization.
Wherein the photoinitiator is a mixture of a visible light initiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine. The photo-polymerization monomer is a mixture of methyl methacrylate monomer with single functionality and pentaerythritol tetraacrylate monomer with multiple functionality according to the mass ratio of 2:1.
The preparation method of the composite material in the embodiment is as follows:
firstly, diaryl ethylene molecules and up-conversion nano particles are added into a mixed solution of a monomer and 4-cyano-4 '-amyl biphenyl (5 CB) liquid crystal, and then a photoinitiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine are added into the mixed solution, and the mixed solution is subjected to ultrasonic dispersion for 60 minutes at 30 ℃, so that the photoinitiator, the photochromic molecules and the up-conversion nano particles are uniformly dispersed in the mixed solution of the monomer and the liquid crystal, and a composite material precursor is prepared.
And irradiating the composite material precursor for 30 seconds under 475 nanometers of coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. Then, a mask is adopted, and the composite material which simultaneously stores a holographic image, a color-changing image and an up-conversion luminescence image is obtained after irradiation for 10 minutes under 365 nanometers and ultraviolet light with the light intensity of 1 milliwatt per square centimeter. Finally, the obtained composite material is irradiated by visible light for 15 hours to carry out post-curing, so that the residual photopolymerization monomer is completely reacted, and the image is fixed.
Example 3
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 2.2 cm by being excited by a dot 808 nanometer laser light source with the diameter of 2 mm, and the area of the obtained images is 121 times of the area of light spots.
The composite material consists of 5wt% of photochromic molecular spiropyran (R 1 The radical is n-amyl, R 2 The radical is hydrogen), 9wt% up-conversion nano-particles (containing 50mol% Yb contained therein) 3+ 、2mol％Er 3+ And 48mol% Y 3+ ) 35% by weight of liquid crystal 4-n-butoxy-4' -cyanobiphenyl (4 OCB), 0.6% by weight of a photoinitiator and 51% by weight of a photopolymerizable monomer were phase-separated by coherent laser polymerization induction.
Wherein the photoinitiator is a mixture of sodium tetraiodotetrachlorofluorescein salt and N-phenylglycine. The photopolymerization monomer is a mixture of mono-functional monomer acrylamide and multi-functional monomer hyperbranched monomer 6361-100 according to the mass ratio of 12:7.
The preparation method of the composite material in the embodiment is as follows:
firstly, spiropyran molecules and up-conversion nano particles are added into a mixed solution of a monomer and 4-N-butoxy-4' -cyanobiphenyl (4 OCB) liquid crystal, and then a photoinitiator tetraiodotetrachlorofluorescein sodium salt and N-phenylglycine are added into the mixed solution, and the mixed solution is subjected to ultrasonic dispersion for 90 minutes at 25 ℃, so that the photoinitiator, the photochromic molecules and the up-conversion nano particles are uniformly dispersed in the mixed solution of the monomer and the liquid crystal, and a composite material precursor is prepared.
And irradiating the composite material precursor for 160 seconds under the coherent laser of 503 nanometers, so that the monofunctional monomer and the polyfunctional monomer undergo free radical polymerization reaction, and the holographic material storing the holographic image is obtained. And then, using a mask plate, and irradiating for 7 minutes under 254 nanometers and ultraviolet light with the light intensity of 1.5 milliwatts per square centimeter to obtain the composite material simultaneously storing the holographic image, the color-changing image and the up-conversion luminescent image. Finally, the obtained composite material is irradiated by visible light for 12 hours to carry out post-curing, so that the residual photopolymerization monomer is completely reacted, and the image is fixed.
Example 4
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 2.8 cm by being excited by a dot 982 nanometer laser light source with the diameter of 4 mm, and the area of the obtained images is 49 times of the area of light spots.
The composite material consists of 9wt% of photochromic molecular spiropyran (R 1 The radicals are 4-cyano-4' -heptyl biphenyl (7 CB), R 2 The radical is hydrogen), 2wt% up-conversion nano-particles (containing 10mol% Yb contained therein) 3+ 、0.2mol％Er 3+ And 89.8mol% Y 3+ ) 40wt% of liquid crystal 4-n-octyloxy-4' -cyanobiphenyl (8 OCB), 1.0% of photoinitiator and 49wt% of photopolymerization monomer are obtained by coherent laser polymerization induced phase separation.
Wherein the photoinitiator is a mixture of ultraviolet light initiator di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2 hydroxy-2-methyl-1-phenyl acetone. The photopolymerization monomer is a mixture of a monofunctional monomer methyl methacrylate and a polyfunctional monomer (a mixture of trimethylolpropane triacrylate and pentaerythritol triacrylate) in a mass ratio of 3:2.
The preparation method of the composite material in the embodiment is as follows:
firstly, spiropyran molecules and up-conversion nano particles are added into a mixed solution of a monomer and 4-N-butoxy-4' -cyanobiphenyl (4 OCB) liquid crystal, and then a photoinitiator tetraiodotetrachlorofluorescein sodium salt and N-phenylglycine are added into the mixed solution, and the mixed solution is subjected to ultrasonic dispersion for 90 minutes at 25 ℃, so that the photoinitiator, the photochromic molecules and the up-conversion nano particles are uniformly dispersed in the mixed solution of the monomer and the liquid crystal, and a composite material precursor is prepared.
And irradiating the composite material precursor for 120 seconds under 512-nanometer coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. And then using a mask plate to irradiate for 10 minutes under 254 nanometers of ultraviolet light with the light intensity of 0.9 milliwatt/square centimeter, so as to obtain the composite material which simultaneously stores the holographic image, the color-changing image and the up-conversion luminescent image. And finally, irradiating the obtained composite material with ultraviolet light for 24 hours to perform post-curing, so that the residual photopolymerization monomer is completely reacted, and fixing the image.
Example 5
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 3 cm by being excited by a dot 980 nm laser light source with the diameter of 2 mm, and the area of the obtained images is 225 times of the area of light spots.
The composite material consists of 4wt% of photochromic molecular diaryl ethylene (structural formula A, ar 1 、Ar 2 Are all I, R 1 、R 2 Groups are tetraphenyl ethylene), 5wt% up-conversion nanoparticles (containing 10mol% Yb contained therein) 3+ 、0.2mol％Er 3+ And 89.8mol% Y 3+ ) 20wt% of liquid crystal P0616A, 1.5% of photoinitiator and 71wt% of photopolymerization monomer are obtained through coherent laser polymerization induced phase separation.
Wherein the photoinitiator is a mixture of ultraviolet light initiator di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2 hydroxy-2-methyl-1-phenyl acetone. The photo-polymerizable monomer is a mixture of monofunctional monomers and polyfunctional monomers according to a mass ratio of 6:5. In the photopolymerization monomer, the monofunctional monomer is a mixture of N, N-dimethylacrylamide and methyl methacrylate, and the polyfunctional monomer is propoxylated trimethylolpropane triacrylate.
The preparation method of the composite material in the embodiment is as follows:
firstly, diaryl ethylene molecules and up-conversion nano particles are added into a mixed solution of a monomer and P0616A liquid crystal, and then a photoinitiator of bis (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2 hydroxy-2-methyl-1-phenyl acetone are added into the mixed solution, and the mixed solution is subjected to ultrasonic dispersion for 120 minutes at 35 ℃ to uniformly disperse the photoinitiator, the photochromic molecules and the up-conversion nano particles in the mixed solution of the monomer and the liquid crystal, so that a composite material precursor is prepared.
And irradiating the composite material precursor for 90 seconds under 532 nanometers of coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. And then using a mask plate to irradiate for 15 minutes under ultraviolet light with the light intensity of 2 milliwatts per square centimeter at 280 nanometers, so as to obtain the composite material which simultaneously stores the holographic image, the color-changing image and the up-conversion luminescence image. And finally, irradiating the obtained composite material with ultraviolet light for 18 hours to perform post-curing, so that the residual photopolymerization monomer is completely reacted, and fixing the image.
The hologram recorded in this embodiment is shown in fig. 2, the color-changing image is shown in fig. 3, and the up-conversion luminescence image is shown in fig. 4.
Example 6
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 2.4 cm by being excited by a dot-shaped 1532 nanometer laser light source with the diameter of 2 mm, and the area of the obtained images is 144 times of the area of light spots.
The composite material consists of 3wt% of photochromic molecule diaryl ethylene (structural formula A, ar 1 、Ar 2 Are all I, R 1 Is methyl, R 2 Benzene ring), 7wt% up-conversionConversion nanoparticles (containing 19.8mol% Yb contained therein) 3+ 、0.2mol％Er 3+ And 80mol% Y 3+ ) 20wt% of liquid crystal P0616A, 1.5% of photoinitiator and 70wt% of photopolymerization monomer are obtained through coherent laser polymerization induced phase separation.
Wherein the photoinitiator is a mixture of a visible light initiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine. The photo-polymerization monomer is a mixture of a monofunctional monomer and a polyfunctional monomer, the mass ratio of the monofunctional monomer to the polyfunctional monomer is 12:11, wherein the monofunctional monomer is a mixture of N, N-dimethylacrylamide and acrylamide, and the polyfunctional monomer is a mixture of ethylene glycol dimethacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
The preparation method of the composite material in the embodiment is as follows:
firstly, diaryl ethylene molecules and up-conversion nano particles are added into a mixed solution of a monomer and P0616A liquid crystal, and then a photoinitiator 3,3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine are added into the mixed solution, and the mixture is subjected to ultrasonic dispersion for 90 minutes at 50 ℃, so that the photoinitiator, the photochromic molecules and the up-conversion nano particles are uniformly dispersed in the mixed solution of the monomer and the liquid crystal, and a precursor of the composite material is prepared.
And irradiating the composite material precursor for 40 seconds under 575 nanometers of coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. And then irradiating the composite material for 5 minutes by using a mask under 305 nanometers of ultraviolet light with the light intensity of 2 milliwatts per square centimeter to obtain the composite material which simultaneously stores the holographic image, the color-changing image and the up-conversion luminescent image. Finally, the obtained composite material is subjected to post-curing by irradiation of visible light for 18 hours, so that the residual photopolymerization monomer is completely reacted, and the image is fixed.
Example 7
The holographic polymer composite material for storing the triple images provided by the embodiment can not only present high-brightness holographic images and color-changing images in the same space position of the material, but also present up-conversion luminescent images with the diameter of 0.3 cm by being excited by a dot 808 nanometer laser light source with the diameter of 4 mm, and the area of the obtained images is about 2 times of the area of light spots.
The composite material consists of 10wt% of photochromic molecule azobenzene (R) 1 Is amino, R 2 Hydrogen), 15wt% up-conversion nanoparticles (containing 19.8mol% Yb contained therein) 3+ 、0.2mol％Er 3+ 、2mol％Tm 3+ And 78mol% Y 3+ ) 20wt% of liquid crystal JC-M-LC-TD, 1.5% of photoinitiator and 55wt% of photopolymerization monomer are obtained by coherent laser polymerization induced phase separation.
Wherein the photoinitiator is a visible light photoinitiator ultraviolet initiator which is a mixture of di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2-hydroxy-2-methyl-1-phenyl acetone.
The photo-polymerization monomer is a mixture of a monofunctional monomer and a polyfunctional monomer, and the mass ratio of the monofunctional monomer to the polyfunctional monomer is 1:1. Wherein the monofunctional monomer is a mixture of N, N-dimethylacrylamide and methacrylic acid, and the polyfunctional monomer is a mixture of ethylene glycol dimethacrylate, pentaerythritol tetraacrylate and hyperbranched monomer 6361-100.
The preparation method of the composite material in the embodiment is as follows:
firstly, adding azobenzene molecules and up-conversion nano particles into a mixed solution of a monomer and JC-M-LC-TD liquid crystal, then adding photo-initiator di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2-hydroxy-2-methyl-1-phenyl acetone into the mixed solution, and performing ultrasonic dispersion for 30 minutes at 44 ℃ to uniformly disperse the photo-initiator, the photochromic molecules and the up-conversion nano particles in the mixed solution of the monomer and the liquid crystal to obtain the composite material precursor.
And irradiating the composite material precursor for 100 seconds under 633 nm coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so as to obtain the holographic material storing the holographic image. Then, a mask is adopted, and the composite material which simultaneously stores a holographic image, a color-changing image and an up-conversion luminescence image is obtained after irradiation for 12 minutes under ultraviolet light with 327 nanometers and light intensity of 2 milliwatts per square centimeter. And finally, irradiating the obtained composite material with ultraviolet light for 16 hours to perform post-curing, so that the residual photopolymerization monomer is completely reacted, and fixing the image.
In addition, other embodiments of the invention are shown in the following table:
table 1: formulations according to other exemplary embodiments of the invention
| Examples | Up-conversion nanoparticles |
| 8 | 65.8mol％Y 3+ 、15mol％Er 3+ 、15mol％Yb 3+ 、4.2mol％Tm 3+ |
| 9 | 69.8mol％Y 3+ 、2mol％Er 3+ 、28mol％Yb 3+ 、0.2mol％Tm 3+ |
| 10 | 40mol％Gd 3+ 、40mol％Y 3+ 、2mol％Er 3+ 、17.8mol％Yb 3+ 、0.2mol％Tm 3+ |
| 11 | 58mol％Gd 3+ 、20mol％Y 3+ 、2mol％Er 3+ 、10mol％Yb 3+ 、10mol％Tm 3+ |
| 12 | 20mol％Gd 3+ 、68mol％Y 3+ 、2mol％Er 3+ 、5mol％Yb 3+ 、5mol％Tm 3+ |
| 13 | 58mol％Gd 3+ 、20mol％Y 3+ 、1.2mol％Er 3+ 、20mol％Yb 3+ 、0.8mol％Tm 3+ |
| 14 | 79.8mol％Y 3+ 、0.2mol％Er 3+ 、18mol％Yb 3+ 、2mol％Tm 3+ |
| 15 | 69.8mol％Y 3+ 、2mol％Er 3+ 、28mol％Yb 3+ 、0.2mol％Tm 3+ |
| 16 | 59.8mol％Y 3+ 、0.2mol％Er 3+ 、30mol％Yb 3+ 、10mol％Tm 3+ |
| 17 | 58mol％Gd 3+ 、20mol％Y 3+ 、2mol％Er 3+ 、10mol％Yb 3+ 、10mol％Tm 3+ |
| 18 | 20mol％Gd 3+ 、68mol％Y 3+ 、2mol％Er 3+ 、5mol％Yb 3+ 、5mol％Tm 3+ |
| 19 | 79.8mol％Y 3+ 、0.2mol％Er 3+ 、10mol％Yb 3+ 、10mol％Tm 3+ |
| 20 | 69.8mol％Y 3+ 、2mol％Er 3+ 、28mol％Yb 3+ 、0.2mol％Tm 3+ |
| 21 | 58mol％Gd 3+ 、20mol％Y 3+ 、2mol％Er 3+ 、10mol％Yb 3+ 、10mol％Tm 3+ |
| 22 | 40mol％Gd 3+ 、40mol％Y 3+ 、2mol％Er 3+ 、17.8mol％Yb 3+ 、0.2mol％Tm 3+ |
Comparative example 1
The composite provided in this comparative example consists of 2wt% of spiropyran (R 1 、R 2 Radicals are hydrogen atoms), 5wt% of up-conversion nanoparticles (which contain 60mol% Y 3+ 、30mol％Yb 3+ 、2mol％Er 3+ And 8mol% Gd 3+ ) 93wt% of the photopolymerizable monomer and 0.2% of the total weight of the photoinitiator were obtained by selectivity.
Wherein the photoinitiator is a mixture of ultraviolet light initiator di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2 hydroxy-2-methyl-1-phenyl acetone. The photopolymerization monomer is a mixture of monofunctional monomer N, N-dimethylacrylamide and polyfunctional monomer ethylene glycol dimethacrylate according to the mass ratio of 3:1.
The preparation method of the composite material in the comparative example is as follows:
firstly, adding spiropyran and up-conversion nano particles into a monomer, then adding a photoinitiator of bis (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2 hydroxy-2-methyl-1-phenyl acetone into the solution, and performing ultrasonic dispersion for 60 minutes at 20 ℃ to ensure that the photoinitiator, the up-conversion nano particles and the photochromic molecules are uniformly dispersed in the monomer, thus preparing the holographic polymer/up-conversion nano particle composite precursor.
And irradiating the precursor of the holographic polymer/up-conversion nanoparticle composite material for 10 seconds under 432-nanometer coherent laser to enable the monofunctional monomer and the polyfunctional monomer to undergo free radical polymerization reaction, so that the holographic material for storing the holographic image cannot be obtained. Then, a mask is adopted, and the composite material which simultaneously stores a holographic image, a color-changing image and an up-conversion luminescence image can not be obtained after the composite material is irradiated for 8 minutes under 365 nanometers and ultraviolet light with the light intensity of 2 milliwatts per square centimeter. And finally, irradiating the obtained composite material with ultraviolet light for 12 hours, and then curing to enable the residual photopolymerization monomer to completely react, so as to fix the image.
In this comparative example, since the liquid crystal is not contained, a phase separation structure and a waveguide structure cannot be formed, up-conversion luminescence does not spread, and a clear hologram image, a color-change image, and an up-conversion luminescence image cannot be obtained.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A holographic polymer composite material for storing triple images is characterized in that,
the composite material is prepared by up-conversion nano particles, liquid crystal and photopolymerization monomers through coherent laser polymerization induced phase separation; in the same spatial position of the composite material, not only can a high-brightness holographic image and a color-changing image be presented under sunlight, but also an up-conversion luminous image can be presented under the excitation of a dot near infrared laser light source; the area of the up-conversion luminous image is 2-225 times of the spot area of the dot near infrared laser;
the composite material comprises: 3-15 wt% of a photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal and 30-74 wt% of a photopolymerization monomer; and the photo initiator accounting for 0.1-5% of the total weight.
2. The holographic polymer composite material for triple image storage according to claim 1, wherein the wavelength of the dot near infrared laser light source is 808-1532 nm, and the spot diameter of the dot near infrared laser light is 0.2-0.4 cm; the up-conversion luminescence image has a diameter of 0.5-3 cm.
3. Holographic polymeric composite material for triple image storage according to claim 1 or 2, wherein said up-conversion nanoparticles are surface ligand modified lanthanide ion doped NaYF 4 ；
The lanthanide ion comprises Yb 3+ At the same time comprise Gd 3+ 、Er 3+ And Tm 3+ The Yb is one of 3+ 、Gd 3+ 、Er 3+ 、Tm 3+ The molar amounts of the ions respectively account for 10-80%, 0-15% and 0-10% of the total molar amount of the lanthanide ions.
4. Holographic polymeric composite material for triple image storage according to claim 1 or 2, wherein said photochromic compound comprises one or more of diarylethenes, spiropyrans, azobenzenes, wherein said diarylethenes have the following structural formula:
wherein Ar is 1 、Ar 2 Each independently selected from any one of the following structural formulas I, II, III, IV, V and VI:
wherein the site marked as a radical attachment site is attached in formula A, B, C, D; and each of the substituents R1, R2 is independently selected from hydrogen, methyl, ethyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or cyanostilbene derivatives;
the structural formula of the spiropyrans is as follows:
the structural formula of the azobenzene is as follows:
in the structural formulas of the spiropyrans and the azobenzene, the substituent groups R1 and R2 are respectively and independently selected from hydrogen, methyl, ethyl, n-amyl, n-hexyl, phenyl, tetraphenyl ethylene, benzothiadiazole groups, coumarin derivatives or cyanostilbene derivatives.
5. Holographic polymeric composite material for triple image storage according to claim 1 or 2, wherein the liquid crystal is one or more of commercial P0616A, 4-n-butyl-4 '-cyanobiphenyl, 4-n-pentyl-4' -cyanobiphenyl, 4-n-heptyl-4 '-cyanobiphenyl, 4-n-octyloxy-4' -cyanobiphenyl, 4-n-pentyl-4 '-cyanobiphenyl, 4-4' -azobisite, cholesteryl benzoate, commercial JC-M-LC-TD.
6. The holographic polymeric composite material for triple image storage of claim 1 or 2, wherein said photopolymerizable monomers comprise monofunctional monomers and polyfunctional monomers;
the monofunctional monomer comprises one or more of N-vinyl pyrrolidone, acrylamide, methacrylamide, N-dimethylacrylamide, isobornyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethyl methacrylate and N-vinyl carbazole;
the multifunctional monomer includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, ethylene glycol dimethacrylate, and commercial hyperbranched monomers 6361-100.
7. Holographic polymeric composite material for triple image storage according to claim 1 or 2, wherein said photoinitiator is an ultraviolet initiator or a visible photoinitiator;
the visible light initiator is a mixture of bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, 3' -carbonylbis (7-diethylaminocoumarin) and N-phenylglycine or a mixture of tetraiodotetrachlorofluorescein sodium salt and N-phenylglycine;
the ultraviolet initiator is a mixture of di (2, 6-dimethoxy benzoyl) -2, 4-trimethyl amyl phosphate and 2-hydroxy-2-methyl-1-phenyl acetone.
8. A method for producing a holographic polymeric composite material for triple image storage according to any of claims 1 to 7, comprising the steps of:
s1: uniformly mixing 3-15 wt% of photochromic compound, 2-15 wt% of up-conversion nano particles, 9-45 wt% of liquid crystal, 30-74 wt% of photopolymerization monomer and 0.1-5% of photoinitiator based on the total weight to obtain a composite material precursor;
s2: packaging the composite material precursor obtained in the step S1 in a liquid crystal box, and adopting coherent laser irradiation to polymerize the photopolymerization monomer to obtain a holographic material stored with a holographic image;
s3: irradiating the holographic material obtained in the step S2 by ultraviolet light through a mask plate to obtain a composite material which stores a holographic image, a color-changing image and an up-conversion image simultaneously; the mask plate is used for defining a color-changing image and an up-conversion luminescence image;
s4: and (3) performing post-curing on the composite material obtained in the step (S3) by adopting visible light or ultraviolet light, and fixing the obtained image.
9. Use of a holographic polymeric composite material for triple image storage according to any of claims 1 to 7 in the field of optical security, optical information storage or display.
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