CN111218017A - Composite film with double image anti-counterfeiting functions and preparation method thereof - Google Patents

Composite film with double image anti-counterfeiting functions and preparation method thereof Download PDF

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CN111218017A
CN111218017A CN202010068645.4A CN202010068645A CN111218017A CN 111218017 A CN111218017 A CN 111218017A CN 202010068645 A CN202010068645 A CN 202010068645A CN 111218017 A CN111218017 A CN 111218017A
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composite film
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CN111218017B (en
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彭海炎
罗文�
解孝林
周兴平
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Huazhong University of Science and Technology
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Abstract

The invention discloses a composite film with double image anti-counterfeiting functions, which comprises 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystals and 30-60 parts of polymers by weight, wherein the modified up-conversion nanoparticles comprise up-conversion nanoparticles with a core-shell structure and a coloring layer coated on the outer side of the up-conversion nanoparticles, the coloring layer is formed by blending silicon dioxide and organic dye, and the mass ratio of the organic dye to the silicon dioxide is 0.01-0.1: 1. The composite film with the double-image anti-counterfeiting function, which is prepared by the invention, has double images of the holographic image and the up-conversion image, and improves the safety of products.

Description

Composite film with double image anti-counterfeiting functions and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a composite film with double image anti-counterfeiting functions and a preparation method thereof.
Background
Upconversion luminescence is a process of absorbing two or more long wavelength photons and converting them into short wavelength photons for emission. A significant feature of the upconversion process is that the absorbed photon energy is much lower than the emitted photon energy, and is therefore also referred to as anti-stokes luminescence. Generally, the most studied upconversion luminescence refers to photoluminescence that generates visible or ultraviolet light under near-infrared or infrared light excitation. Among them, rare earth ion doped up-conversion luminescence has become the focus of research in the field of luminescent materials at present due to its excellent luminescence properties such as narrow spectrum, high luminescent color purity, high conversion efficiency, wide emission region, long fluorescence lifetime, etc.
The counterfeit products are infiltrated into various fields such as medicine, food and the like which are concerned with the life health of people, and become important hidden dangers of national economic safety and social stability. The laser holography technology based on photopolymerization is one of the important technologies for high-end anti-counterfeiting. The laser holographic technology has high requirements on equipment and great technical difficulty; the anti-counterfeiting material prepared by the laser holography technology can present a three-dimensional color holographic image identified by naked eyes under natural light, is convenient for common people to identify and has good anti-counterfeiting effect. However, holographic images lack concealment and the anti-counterfeiting effect needs to be enhanced. The up-conversion luminescent material can be used for preparing a concealed anti-counterfeiting material (Chinese patents CN105885845A and CN 105082810A). However, the existing up-conversion luminescent material anti-counterfeiting needs professional equipment and does not have the convenience of holographic anti-counterfeiting.
CN108148331B discloses a composite material with dual image functions, which can observe a holographic image recognized by naked eyes under natural light, and can observe fluorescence visible by naked eyes under near-infrared laser, but the development of high technology makes the forms of counterfeit and shoddy products more abundant, and the security of the genuine products of the products is difficult to be ensured by the holographic image and single fluorescence.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a composite film with double image anti-counterfeiting functions, so that the composite film has the double image anti-counterfeiting functions of a holographic image and an up-conversion image, and the safety of a product quality product is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the composite film with the double image anti-counterfeiting function comprises, by weight, 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystals and 30-60 parts of polymers, wherein the modified up-conversion nanoparticle structure comprises up-conversion nanoparticles with a core-shell structure and a coloring layer coated on the outer side of the up-conversion nanoparticles, the coloring layer is formed by blending silicon dioxide and organic dye, and the mass ratio of the organic dye in the silicon dioxide is 0.01-0.1: 1.
In the scheme, a uniform dispersion liquid consisting of a polymer, a liquid crystal and modified up-conversion nanoparticles is injected into a transparent liquid crystal box, the transparent liquid crystal box is placed in a laser interference field to prepare a holographic image, then a composite film is placed under ultraviolet light, an organic dye and the up-conversion nanoparticles with a core-shell structure are coated by silicon dioxide, so that the energy of the up-conversion nanoparticles with the core-shell structure is partially absorbed by the organic dye and emits visible light with a wavelength different from the light emitting wavelength of the up-conversion nanoparticles, the up-conversion light emitting color is adjusted, when the composite film is irradiated by strong ultraviolet light, the organic dye structure is damaged and photobleaching is carried out, the light emitting color is changed into the original light emitting color of the up-conversion nanoparticles again, and the composite film blocked by a photomask plate is different from the composite film not blocked by the photomask plate due to the absorption, thus, the up-conversion image is prepared, and the composite film has the double image anti-counterfeiting function of the holographic image and the up-conversion image. The coating ratio of the coloring layer to the up-conversion nano particles of the core-shell structure is 100%.
Further, the organic phase-change material comprises, by weight, 20-30 parts of modified up-conversion nanoparticles, 20-30 parts of liquid crystals and 40-50 parts of polymers.
The liquid crystal display further comprises 25 parts of modified up-conversion nano particles, 25 parts of liquid crystal and 45 parts of polymer in parts by weight.
Further, the mass ratio of the organic dye to the silica is 0.05: 1.
Further, the up-conversion nanoparticles with the core-shell structure comprise, by weight, 30-50 parts of a luminescent active core and 50-70 parts of a luminescent inert shell, wherein the luminescent active core is lanthanide ion-doped NaYF4Said NaYF4The molar ratio to the lanthanide ion is 2-6: 3, the lanthanide ion comprises a mol/L Yb3+While including b mol/L Er3+And/or a Tm of 0.03-a-b mol/L3+At least one of; a is 0.01 to 0.02; b is 0 to 0.01; the luminous inert shell is NaYF4. The lanthanide ion is Yb3+And Er3+Or is Yb3+And Tm3+Or is Yb3+、Er3+And Tm3+Three composition forms.
The specific preparation method of the core-shell structure up-conversion nano particle comprises the following steps:
k1: adding 0.2-0.75mol/L of sodium salt of unsaturated carboxylic acid to unsaturated carboxylic acid and octadecene, and adding 0.02-0.06mol/L of rare earth oleate (Y (C)17H33CO2)3) Adding lanthanide ion into the matrix, heating and stirring at 100-120 deg.C in inert gas atmosphere to dissolveAdding 0.2-0.8mol/L ammonium fluoride, rapidly heating to 290-330 ℃, continuing to react for 30-70min, cooling and centrifuging to obtain a supernatant I, adding a precipitator into the supernatant I, taking precipitate as luminescent active nucleus, dissolving the luminescent active nucleus in a nonpolar solvent to obtain a mixture A, wherein the mixture A is a dispersion liquid of the luminescent active nucleus; the precipitator is any one of ethanol and propanol; the nonpolar solvent is one of cyclohexane, normal hexane and toluene;
k2: adding 0.2-0.7mol/L of sodium salt of unsaturated carboxylic acid and 0.02-0.09mol/L of rare earth oleate (Y (C) to unsaturated carboxylic acid and octadecene17H33CO2)3) Heating and stirring a substrate in an inert gas atmosphere, adding 0.15-0.45mol/L ammonium fluoride, rapidly heating to 180-240 ℃, continuously reacting for 30-70min, cooling, centrifuging to obtain a supernatant II, adding a precipitator into the supernatant II, taking a precipitate, namely a precursor of a luminescent inert shell, dissolving the precursor of the luminescent inert shell in a nonpolar solvent to obtain a mixture B, namely a precursor dispersion liquid of the luminescent inert shell;
k3: adding the mixture A in the step S1 and the mixture B in the step S2 into unsaturated carboxylic acid and octadecene, rapidly heating to 290-330 ℃ under the condition of inert gas, reacting for 30-70min, and cooling to room temperature to obtain a mixed solution C; and centrifuging the mixed solution C to obtain supernatant, precipitating the supernatant by adopting a precipitator, and taking the precipitate to obtain the upconversion nanoparticles with the core-shell structure.
Further, the organic dye comprises one or more of fluorescein isothiocyanate, rhodamine B, rhodamine isothiocyanate B, acid rose bengal B and rose bengal.
Further, the polymer is formed by polymerizing a monofunctional monomer and a polyfunctional crosslinking agent; the single-functionality monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-methylolacrylamide, N-diethylacrylamide, isooctyl acrylate, vinyl acetate, methyl methacrylate and tert-butyl acrylate;
the multifunctional cross-linking agent is one or more of ethylene glycol dimethacrylate, glyceryl dimethacrylate, bisphenol A glycerol dimethacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol dimethacrylate and commercialized hyperbranched monomer 6361-100;
the monofunctional monomer means that the number of functional groups capable of participating in reaction in the monomer is one; the multifunctional crosslinking agent means that the number of functional groups capable of participating in reaction in the crosslinking agent is at least 2.
Further, the liquid crystal is one or more of P0616A, 4-n-octyl-4 ' -cyanobiphenyl, 4-octyloxy-4 ' -cyanobiphenyl and 4-n-heptyl-4 ' -cyanobiphenyl. The P0616A comprises at least one of 56.5% of 4-n-pentyl-4 '-cyanobiphenyl, 25.1% of 4-n-heptyl-4' -cyanobiphenyl, 11.4% of 4-octyloxy-4 '-cyanobiphenyl and 7.0% of 4-n-pentyl-4' -cyanobiphenyl.
The invention also aims to provide a preparation method of the composite film with double image anti-counterfeiting functions, which comprises the following steps:
s1: preparing modified up-conversion nanoparticles;
(1) dispersing 0.1-1.0 g of up-conversion nanoparticles with a core-shell structure in 10-50 mL of a nonpolar solvent, adding 0.5-5.0 mmol of surfactant while stirring, adding 20-200 mu L of ammonia water and 0.01-0.8 mmol of organic dye after the solution is transparent, reacting for 30-60 min at room temperature, adding tetraethyl silicate, and reacting for 24-72 h at room temperature to obtain a mixture C; the surfactant is one of polyoxyethylene nonyl phenol polyether, nonoxynol ether, lauryl amine polyoxyethylene ether and coconut diethanolamide;
(2) adding 20-200 mu L of ammonia water and 50-200 mu L of silane coupling agent into the mixture C obtained in the step (1), reacting for 2-10 hours at room temperature to obtain a mixture D, centrifuging the mixed solution D, and taking a precipitate, wherein the precipitate is the modified up-conversion nanoparticles; the silane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and allyltrimethoxysilane.
S2: uniformly mixing 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystal, 30-60 parts of monofunctional monomer, 10-20 parts of polyfunctional cross-linking agent and 0.1-2 parts of photoinitiation polymerization inhibitor, and coating the mixture on the surface of a transparent glass sheet or pouring the mixture into a transparent liquid crystal box through siphoning;
s3: placing the transparent glass sheet or the transparent liquid crystal box in the step S2 into a single beam of light with the light intensity of 0.1-6mW/cm2In an interference light field with the wavelength of 440-480nm or 510-545nm, the illumination time is 5-300s, and holographic image storage is carried out through photo-initiated free radical polymerization to obtain a film with holographic images; the interference light field consists of two beams of light with the same wavelength, wherein one beam of light passes through a light space modulator or an actual object to record image information required to be stored, and interferes with the other beam of light at the position where the other beam of light is generated on the transparent glass sheet or the transparent liquid crystal box;
s4: placing the holographic image film obtained in the step S3 under a photomask, curing by blue light, and then using light intensity of 10-100mW/cm2The ultraviolet lamp is used for illumination, the illumination time is 1-100min, and the composite film with the double anti-counterfeiting functions of the holographic image and the up-conversion luminescence image is obtained. The shape of the up-conversion light-emitting pattern is consistent with the pattern of the photomask.
In step S1, the unsaturated carboxylic acid is one of 9-hexadecenoic acid, 10-heptadecenoic acid and oleic acid.
Further, the photoinitiation polymerization inhibitor is one or more of a mixture of 3, 3' -carbonyl bis (7-diethylamine coumarin) and N-phenylglycine and a mixture of tetrachlorotetraiodofluorescein and N-phenylglycine.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by regulating and controlling the range of the modified up-conversion nano particles, the liquid crystal and the polymer, the prepared composite film with the double-image anti-counterfeiting function has bright and clear holographic images and up-conversion image double images, and the safety of the product is improved.
Drawings
FIG. 1 is a holographic image of the composite film described in example 1 under white light illumination;
FIG. 2 is an upconversion luminescence image of the composite film described in example 1 under 980nm2W near infrared illumination;
FIG. 3 is a graph of the upconversion luminescence spectra of the composite film of example 1 after exposure to UV light, under 980nm2W light, in the exposed and unexposed areas;
FIG. 4 is a graph of the upconversion luminescence spectra of the composite film of example 5 after exposure to UV light, under 980nm2W light, in the exposed and unexposed areas;
FIG. 5 is a CIE chromaticity diagram for varying amounts of organic dye in the silica;
FIG. 6 is a CIE chromaticity diagram of the up-converted luminescence of the exposed and unexposed regions of the composite film of comparative example 1 under 980nm2W illumination after exposure to UV light;
FIG. 7 shows the up-conversion luminescence of the composite film of comparative example 7 under 980nm near infrared light after UV exposure.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A composite film with a dual image anti-counterfeiting function comprises 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystals and 30-60 parts of polymers, wherein the modified up-conversion nanoparticle structure comprises up-conversion nanoparticles with a core-shell structure and a coloring layer coated on the outer side of the up-conversion nanoparticles, the coloring layer is formed by blending silicon dioxide and organic dye, and the mass ratio of the organic dye in the silicon dioxide is 0.01-0.1: 1.
In the above composite film, when the kinds of the liquid crystal, the polymer and the organic dye are selected from one or more kinds within the scope of the claims of the present invention, there is no great influence on the preparation of the composite film having a hologram image and an up-conversion image dual image.
In the preparation method of the upconversion nanoparticles with the core-shell structure in the scope of the present invention, the inventors have found through extensive research that when one or more of the types and the scope of the luminescent active core and the luminescent inert shell are selected within the scope of the claims of the present invention, the composite film having the holographic image and the upconversion image is prepared with little influence.
In the preparation method of the modified up-conversion nanoparticles in the preparation method of the composite film with the double-image anti-counterfeiting function, the inventor finds that the unsaturated carboxylic acid, the surfactant, the precipitating agent, the non-polar solvent and the silane coupling agent in the scope of the application have little influence on the preparation of the composite film with the holographic image and the up-conversion image.
Example 1
A composite film with double image anti-counterfeiting functions specifically comprises the following steps:
s1: preparing modified up-conversion nanoparticles;
(1) dispersing 0.5g of up-conversion nanoparticles with a core-shell structure in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.0058g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 290 mu L of tetraethyl silicate (the molar concentration is 1mol/L), and reacting for 30h at room temperature to obtain a mixture C;
(2) and (2) adding 20 mu L of ammonia water, 50 mu L of silane coupling agent and 3-aminopropyltriethoxysilane into the mixture C obtained in the step (1), reacting for 2-10 hours at room temperature to obtain a mixture D, centrifuging the mixed solution D, and taking a precipitate, wherein the precipitate is the modified upconversion nanoparticles.
S2: 0.25g of modified up-conversion nano particles, 0.25g of liquid crystal P0616A, 0.35g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.05g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.05g of N-phenylglycine are uniformly mixed according to the parts by weight and coated on the surface of a transparent glass sheet;
s3: placing the transparent glass sheet obtained in the step S2 in a single beam with the light intensity of 0.1mW/cm2In an interference light field with the wavelength of 440nm, the illumination time is 5s, and holographic image storage is carried out through photo-initiated free radical polymerization to obtain a film with holographic images;
s4: curing the unreacted monomers of the holographic image film obtained in the step S3 by adopting blue light, then placing the film under a photomask plate, and using light intensity of 10mW/cm2The ultraviolet lamp is used for illumination, the illumination time is 5min, and the composite film with the double anti-counterfeiting functions of the holographic image and the up-conversion luminescence image is obtained, wherein the thickness of the composite film is 30 micrometers.
Example 2
Example 2 differs from example 1 in that:
s2: 0.1g of modified up-conversion nanoparticles, 0.4g of liquid crystal P0616A, 0.5g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.01g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.01g of N-phenylglycine were uniformly mixed and coated on the surface of a transparent glass sheet.
The rest of the procedure was the same as in example 1.
Example 3
Example 3 differs from example 1 in that:
s2: 0.2g of modified up-conversion nanoparticles, 0.2g of liquid crystal P0616A, 0.40g of methyl methacrylate, 0.10g of ethylene glycol dimethacrylate, 0.01g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.01g N-phenylglycine were uniformly mixed and mixed, and the mixture was coated on the surface of a transparent glass sheet.
Example 4
Example 5 differs from example 1 in that:
s2: 0.3g of modified up-conversion nanoparticles, 0.3g of liquid crystal P0616A, 0.3g of methyl methacrylate, 0.10g of ethylene glycol dimethacrylate, 0.01g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.01g N-phenylglycine were uniformly mixed and mixed, and the mixture was coated on the surface of a transparent glass sheet.
Example 5
Example 5 differs from example 1 in that:
s2: 0.4g of modified up-conversion nanoparticles, 0.05g of liquid crystal P0616A, 0.2g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.01g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 1 part of N-phenylglycine are uniformly mixed and mixed, and the mixture is coated on the surface of a transparent glass sheet.
Example 6
Example 6 differs from example 1 in that:
s1: preparing modified up-conversion nanoparticles;
(1) and (2) dispersing 0.5g of core-shell structured up-conversion nanoparticles in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.0116g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 290 mu L of tetraethyl silicate, and reacting for 30h at room temperature to obtain a mixture C.
Example 7
Example 7 differs from example 1 in that:
(1) dispersing 0.5g of core-shell structured up-conversion nanoparticles in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.00012g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 290 mu L of tetraethyl silicate, and reacting for 30h at room temperature to obtain a mixture C.
Comparative example 1
Comparative example 1 differs from example 1 in that:
s2: 0.05g of modified up-conversion nanoparticles, 0.25g of liquid crystal P0616A, 0.35g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.05g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.05g of N-phenylglycine were uniformly mixed and coated on the surface of a transparent glass sheet.
Comparative example 2
Comparative example 2 differs from example 1 in that:
s2: 0.45g of modified up-conversion nanoparticles, 0.25g of liquid crystal P0616A, 0.30g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.005g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.005g of N-phenylglycine were uniformly mixed and mixed, and coated on the surface of a transparent glass sheet.
Comparative example 3
Comparative example 3 differs from example 1 in that:
s2: 0.25g of modified upconversion nanoparticles, 0.15g of liquid crystal P0616A, 0.60g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.05g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.05g of N-phenylglycine were uniformly mixed and coated on the surface of a transparent glass sheet.
Comparative example 4
Comparative example 4 differs from example 1 in that:
s1: preparing modified up-conversion nanoparticles;
(1) dispersing 0.02g of core-shell structured up-conversion nanoparticles in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.00018g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 870 mu L of tetraethyl silicate, and reacting for 30h at room temperature to obtain a mixture C.
Comparative example 5
Comparative example 5 differs from example 1 in that:
s1: preparing modified up-conversion nanoparticles;
dispersing 0.5g of core-shell structured up-conversion nanoparticles in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.0232g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 290 mu L of tetraethyl silicate, and reacting for 30h at room temperature to obtain a mixture C.
Comparative example 6
S1: preparing modified up-conversion nanoparticles;
dispersing 0.45g of up-conversion nanocrystalline in CN108148331B patent in 25mL of nonpolar solvent n-hexane, adding 0.5mmol of surfactant polyoxyethylene nonylphenol polyether under stirring, adding 50 mu L of ammonia water and 0.0058g of organic dye fluorescein isothiocyanate after the solution is transparent, reacting for 30min at room temperature, adding 290 mu L of tetraethyl silicate, and reacting for 30h at room temperature to obtain a mixture C.
Comparative example 7
The raw materials of patent CN108148331B are adopted to prepare the composite material, and the specific preparation process is as follows:
s1: uniformly mixing and mixing 0.35g of methyl methacrylate, 0.10g of ethylene glycol dimethacrylate, 0.25g of liquid crystal P0616A, 0.25g of up-conversion nanocrystal, 0.05g of 3, 3' -carbonylbis (7-diethylamine coumarin) and 0.05g N-phenylglycine, and coating the mixture on the surface of a transparent glass sheet;
s2: placing the transparent glass sheet obtained in the step S1 in a single beam with the light intensity of 0.1mW/cm2In an interference light field with the wavelength of 440nm, the illumination time is 5s, and holographic image storage is carried out through photo-initiated free radical polymerization to obtain a film with holographic images;
s3: placing the holographic image film obtained in the step S2 under a photomask, curing the unreacted monomers for 300S by adopting blue light, and then using light intensity of 10mW/cm2The ultraviolet lamp is used for illumination, and the illumination time is 5min, so that the composite film with the holographic image and up-conversion luminescence function is obtained.
Application example
Selecting any one group of composite films with the double anti-counterfeiting functions of the holographic images and the up-conversion luminescence images prepared in the embodiments 1 to 7 and placing the selected composite films under white light, taking the embodiment 1 as an example, obtaining the holographic images as shown in figure 1, wherein clear holographic images of the composite films can be seen in figure 1; the composite film was then placed under 980nm near infrared to obtain an up-converted luminescence image, which can be seen in fig. 2, as shown in fig. 2.
After the composite films in examples 1 and 5 are exposed to ultraviolet light, the up-conversion luminescence spectrograms of the exposed area and the unexposed area under the illumination of 980nm2W are obtained, as shown in fig. 3 and 4 respectively, it can be clearly seen from fig. 3 that in the ultraviolet light irradiation part, the dye molecules are destroyed, the up-conversion luminescence is changed into the blue luminescence of the nano particles, and the conversion luminescence of the part which is not irradiated by the ultraviolet light is absorbed by the dye and is changed into the yellow-green luminescence.
As is clear from fig. 4, when the amount of the added modified upconversion nanoparticles is higher under the same excitation light, the total amount of the dye is also increased, resulting in an increase in the luminescence amount of the dye-absorbing nanoparticles, and the blue region on which luminescence is converted can be completely absorbed by the dye and the apparent color change is larger compared to the composite film in example 1.
The composite films prepared in examples 1, 6 and 7 were subjected to the CIE test to obtain CIE chromaticity diagram as shown in fig. 5, and the shift of the converted luminescent color on the CIE chromaticity diagram was larger as the content of the organic dye in the modified upconversion nanoparticles was increased within a certain range.
The CIE chromaticity diagram of the up-conversion luminescence of the exposed area and the unexposed area under 980nm2W illumination after the composite film obtained in the comparative example 1 is exposed to ultraviolet light is shown in FIG. 6, and as can be seen from FIG. 6, the content of the modified up-conversion nanoparticles is too low, the exciting light required for reaching the light intensity recognizable by human eyes is too strong, the color conversion capability of the dye on the up-conversion luminescence is limited, the color contrast is too low, and the recognizable up-conversion image is difficult to prepare.
After the composite film in comparative example 7 is subjected to ultraviolet exposure, an up-conversion luminescence image under 980nm near-infrared light irradiation is shown in fig. 7, and as can be seen from fig. 7, because the up-conversion nanocrystals are not modified by a dye, in the composite film with the holographic image and the up-conversion luminescence function prepared by the method, the up-conversion function only has a single up-conversion luminescence color, and under 980nm near-infrared light irradiation, only a single luminescence can be seen, but no up-conversion image can be obtained.
The diffraction efficiency and the CIE coordinate offset before and after ultraviolet exposure of the composite films having the dual anti-counterfeit function of the hologram image and the up-conversion luminescence image prepared in examples 1 to 7 were measured, and the obtained diffraction efficiency and the CIE coordinate offset before and after ultraviolet exposure are shown in table 1 below.
Diffraction efficiency measurement method: and irradiating a laser beam on the polymer film, wherein the ratio of diffracted light to the sum of transmitted light and diffracted light is higher.
TABLE 1 diffraction efficiency and CIE coordinate offset before and after UV Exposure
Figure BDA0002376703970000091
Figure BDA0002376703970000101
Analyzing the data of examples 1-5, it can be seen that, with the components and contents in the range of the present application, a composite film with dual image anti-counterfeiting function of holographic image and up-conversion luminescence image can be prepared, and when the contents of the modified up-conversion nanoparticles, the liquid crystal and the polymer are properly increased, the definition and brightness of the up-conversion image and the holographic image are increased, but when the content of the modified up-conversion nanoparticles is increased to more than 30 parts (example 5), the brightness of the up-conversion image is too high, which affects the imaging effect of the holographic image, and a clear up-conversion image can be prepared, but the brightness of the holographic image is reduced; when the content of the polymer is increased to 50 parts or more (example 2), the diffraction efficiency is decreased due to the excessively high content of the polymer, the shift of the upconversion luminescence to the red region becomes large, x is increased, y is decreased, and a clear upconversion image can be prepared, but the brightness of the hologram image is decreased.
When the content of the polymer is continuously increased, for example, 70 parts of the polymer in comparative example 3 is added, since the diffraction efficiency of the holographic image depends on the refractive index difference between the bright area and the dark area after the photopolymerization process, when the content of the photoinitiated polymerization inhibitor is too low, the phase separation effect is poor during the photopolymerization process, and meanwhile, when the content of the liquid crystal is too low, the refractive index difference between the dark area and the bright area is small, the diffraction efficiency of the holographic image is low, and a recognizable holographic image composite film cannot be prepared. When the proportion of the modified up-conversion nanoparticles is too high, for example, increased to 45 parts in comparative example 2, the degree of phase separation is reduced during photopolymerization, resulting in too low diffraction efficiency of the holographic image, and the prepared holographic image cannot be effectively identified. When the proportion of the modified upconversion nanoparticles is too low, such as 5 parts in comparative example 1, the content of the modified upconversion nanoparticles is too low, so that the excitation light required for reaching the light intensity recognizable by human eyes is too strong, the upconversion luminescence color conversion capability of the dye to the upconversion luminescence is limited, the color contrast is too low, and a recognizable upconversion image is difficult to prepare. Therefore, the preferable concentration is 20-30 parts of modified up-conversion nano particles, 20-30 parts of liquid crystal and 40-50 parts of polymer; more preferably 25 parts of modified up-conversion nanoparticles, 25 parts of liquid crystals and 45 parts of polymers.
Analyzing the data of examples 1, 6 and 7, it can be seen that when the mass percentage of the organic dye in the silica is gradually increased, the diffraction efficiency is kept at a higher value, the shift distance of the CIE coordinates is increased, the difference of the up-conversion luminescent color is increased, the prepared dual anti-counterfeiting image has bright and clear holographic images and up-conversion images, but when the dye content exceeds 5%, the aggregation degree is increased, and the luminescent intensity is gradually reduced; when the mass percentage of the organic dye is further increased, for example, to 20% in comparative example 5, there is an aggregation-induced quenching effect of the dye molecules due to too high aggregation of the organic dye, and after absorbing the luminescence of the upconversion nanoparticles, the emitted visible upconversion light intensity is too low to achieve a visible upconversion image. When the mass percentage of the organic dye is reduced, for example, to 0.05% in comparative example 4, the organic dye content of the prepared composite film is too low, the luminescence absorption of the upconversion nanoparticles is small, the degree of change of the luminescence color is small, and the organic dye content cannot be used for realizing a recognizable upconversion luminescence image. Therefore, the mass percentage of the organic dye in the silica is preferably 0.1% to 10%.
When the coloring layer in comparative example 6 is coated on the outer layer of the upconversion nanoparticles with the non-core-shell structure, since the composite film does not use the upconversion nanoparticles with the core-shell structure, the upconversion luminescence intensity is low, and the prepared composite film has low upconversion luminescence image definition.
When the composite film having the holographic image and the upconversion luminescence function is prepared by using the upconversion nanocrystal in comparative example 7, since the upconversion nanocrystal is not modified by a dye, the upconversion function of the composite film having the holographic image and the upconversion luminescence function prepared by the method has only a single upconversion luminescence color, and only a single luminescence can be seen but no upconversion image can be obtained under excitation of 980nm near-infrared light.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The composite film with the double image anti-counterfeiting function is characterized by comprising 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystal and 30-60 parts of polymer in parts by weight, wherein the modified up-conversion nanoparticle structure comprises up-conversion nanoparticles with a core-shell structure and a coloring layer coated on the outer side of the up-conversion nanoparticles, the coloring layer is formed by blending silicon dioxide and organic dye, and the mass ratio of the organic dye to the silicon dioxide is 0.01-0.1: 1.
2. The composite film with double image anti-counterfeiting function according to claim 1, which comprises 20-30 parts by weight of modified up-conversion nanoparticles, 20-30 parts by weight of liquid crystal and 40-50 parts by weight of polymer.
3. The composite film with double image anti-counterfeiting function according to claim 1, which comprises 25 parts by weight of modified up-conversion nanoparticles, 25 parts by weight of liquid crystals and 45 parts by weight of polymer.
4. The composite film with dual image anti-counterfeiting function according to claim 1, wherein the mass ratio of the organic dye to the silica is 0.05: 1.
5. The composition of claim 1 for dual image securityThe film is characterized in that the up-conversion nano particles with the core-shell structure comprise, by weight, 30-50 parts of luminescent active cores and 50-70 parts of luminescent inert shells, wherein the luminescent active cores are lanthanide ion-doped NaYF4Said NaYF4The molar ratio to the lanthanide ion is 2-6: 3, the lanthanide ion comprises a mol/L Yb3+While including b mol/L Er3+And/or a Tm of 0.03-a-b mol/L3+At least one of; a is 0.01 to 0.02; b is 0 to 0.01; the luminous inert shell is NaYF4。
6. The composite film with double image anti-counterfeiting function according to claim 1, wherein the organic dye comprises one or more of fluorescein isothiocyanate, rhodamine B isothiocyanate, acid rose bengal B and rose bengal.
7. The composite film with dual image anti-counterfeiting function according to claim 1, wherein the polymer is formed by polymerization reaction of a monofunctional monomer and a polyfunctional crosslinking agent; the single-functionality monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-methylolacrylamide, N-diethylacrylamide, isooctyl acrylate, vinyl acetate, methyl methacrylate and tert-butyl acrylate;
the multifunctional cross-linking agent is one or more of ethylene glycol dimethacrylate, glyceryl dimethacrylate, bisphenol A glycerol dimethacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol dimethacrylate and commercialized hyperbranched monomer 6361-100.
8. The composite film with dual image anti-counterfeiting function according to claim 1, wherein the liquid crystal is one or more of P0616A, 4-n-octyl-4 ' -cyanobiphenyl, 4-octyloxy-4 ' -cyanobiphenyl and 4-n-heptyl-4 ' -cyanobiphenyl.
9. The preparation method of the composite film with the dual-image anti-counterfeiting function, which is disclosed by any one of claims 1 to 8, is characterized by comprising the following steps of:
s1: preparing modified up-conversion nanoparticles;
s2: uniformly mixing 10-40 parts of modified up-conversion nanoparticles, 5-40 parts of liquid crystal, 30-60 parts of monofunctional monomer, 10-20 parts of polyfunctional cross-linking agent and 0.1-2 parts of photoinitiation polymerization inhibitor, and coating the mixture on the surface of a transparent glass sheet or pouring the mixture into a transparent liquid crystal box through siphoning;
s3: placing the transparent glass sheet or the transparent liquid crystal box in the step S2 into a single beam of light with the light intensity of 0.1-6mW/cm2In an interference light field with the wavelength of 440-480nm or 510-545nm, the illumination time is 5-300s, and holographic image storage is carried out through photo-initiated free radical polymerization to obtain a film with holographic images;
s4: placing the holographic image film obtained in the step S3 under a photomask, curing by blue light, and then using light intensity of 10-100mW/cm2The ultraviolet lamp is used for illumination, the illumination time is 1-100min, and the composite film with the double anti-counterfeiting functions of the holographic image and the up-conversion luminescence image is obtained.
10. The method for preparing a composite film with dual image anti-counterfeiting function according to claim 9, wherein the photoinitiation polymerization inhibitor is one or more of a mixture of 3, 3' -carbonylbis (7-diethylaminocoumarin) and N-phenylglycine and a mixture of tetrachlorotetraiodofluorescein and N-phenylglycine.
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