CN115044251B - Multicolor fluorescent ink based on light-operated nano particles and preparation method thereof - Google Patents
Multicolor fluorescent ink based on light-operated nano particles and preparation method thereof Download PDFInfo
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- CN115044251B CN115044251B CN202210275788.1A CN202210275788A CN115044251B CN 115044251 B CN115044251 B CN 115044251B CN 202210275788 A CN202210275788 A CN 202210275788A CN 115044251 B CN115044251 B CN 115044251B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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Abstract
The invention discloses fluorescent ink based on light-operated nano particles, which is an aqueous solution containing a photoacid compound, polyethyleneimine and fluorescent dye; and (3) polymerizing the photoacid compound and the polyethyleneimine to form spherical nano particles under the light irradiation of 420+/-10 nm of the fluorescent ink, wrapping fluorescent dye molecules in the spherical nano particles, removing the light irradiation, placing the solution in a dark place to avoid light, and reversely changing the nano particle structure formed by the photoacid compound and the polyethyleneimine. The invention also discloses a preparation method of the fluorescent ink based on the light-operated nano particles. The fluorescent ink has double excitation response, firstly, the fluorescent ink can trigger color development after being irradiated by 420nm light, and then, the color can be seen after being excited by 365nm ultraviolet light, so that the safety anti-counterfeiting grade can be obviously improved when the fluorescent ink is applied to the anti-counterfeiting field.
Description
Technical Field
The invention relates to multicolor fluorescent ink based on light-operated nano particles and also relates to a preparation method of the fluorescent ink.
Background
The anti-counterfeiting technology is taken as an important information safety protection measure and plays a very important role in national defense, economy and daily life. The anti-counterfeiting technology used at present mainly comprises the following steps: fluorescent anti-counterfeiting, nuclear track anti-counterfeiting, laser holographic anti-counterfeiting, magnetic anti-counterfeiting and the like, and the anti-counterfeiting technology has wide application in currency circulation, labels and important documents. Fluorescent anti-counterfeiting has the advantages of good stability, simplicity in printing, low cost and the like, and becomes the most common anti-counterfeiting measure. Fluorescent ink based on fluorescent anti-counterfeiting technology is an important component of fluorescent anti-counterfeiting technology. The traditional fluorescent anti-counterfeiting ink is often prepared by methods of organic phase solvent synthesis, nanocrystal instrument encapsulation and the like, and has the problem of complex manufacturing process. The anti-counterfeiting mechanism is based on a single-stage anti-counterfeiting technology, namely ink is invisible under natural light and can be displayed under ultraviolet or near infrared excitation light, and the encryption mode is easily replaced by fluorescent materials with similar emission characteristics, so that the encryption level is reduced, and the anti-counterfeiting performance is lower. Moreover, the traditional fluorescent anti-counterfeiting ink is always only in a fixed form, and has no color development and erasing processes, so that the traditional fluorescent anti-counterfeiting ink is easy to crack and recognize.
Disclosure of Invention
The invention aims to: the invention aims to provide fluorescent ink with double excitation response and high anti-counterfeiting performance, and the fluorescent ink can excite color development when color development is needed and can not perform fluorescent color development when color development is not needed; another object of the present invention is to provide a method for preparing the fluorescent ink.
The technical scheme is as follows: the multicolor fluorescent ink based on the light-operated nano particles is an aqueous solution containing a photoacid compound, polyethyleneimine and fluorescent dye; and (3) polymerizing the photoacid compound and the polyethyleneimine to form spherical nano particles under the light irradiation of 420+/-10 nm of the fluorescent ink, wrapping fluorescent dye molecules in the spherical nano particles, removing the light irradiation, placing the solution in a dark place to avoid light, and reversely changing the nano particle structure formed by the photoacid compound and the polyethyleneimine.
Irradiating for 10 minutes under 420nm light to obtain spherical nano particles; the spherical nano particles are converted into square nano particles after being placed in a dark place for 20 minutes, and the chemical structural formula of the photoacid compound is as follows:the photoacid compound is converted into an anionic amphiphilic compound after 420nm light irradiation, and the structural formula is changed into: />The reaction equation is:
the structural formula of the polyethyleneimine is as follows:
zwitterionic (having both positively and negatively charged ends) photoacid and cationic polyethyleneimine initially exist in the free state in aqueous solution, upon activation by irradiation with 420nm light, the photoacid molecule isomerizes to an anionic sulfonic spiropyran compound; due to the strong electrostatic interaction between the negatively charged photoacid isomerism molecules and the positively charged polyethyleneimine molecules and the hydrophilic and hydrophobic properties of the two molecules, the two molecules can construct unsteady spherical supermolecule nano particles; removing 420nm light irradiation to place the solution in a completely dark place, and spontaneously converting the photo-acid isomerism molecules into photo-acid molecules in an initial state, wherein part of photo-acid isomerism molecules can still keep an isomerism state in the dark due to the positive charge of the polyethyleneimine molecules, and the nano particles are not completely dissociated but are mutually combined to be converted into larger square nano particles; after 420nm reciprocating light irradiation, the assembled state of the nanoparticles in the solution can be cycled between a spherical nanoparticle assembled state and a square nanoparticle assembled state. Adding fluorescent dye into the precursor liquid before assembly, using 420nm illumination to drive nano particles to assemble, wrapping dye molecules into nano particles, enabling an assembly system carrying fluorescent dye molecules to emit fluorescence with corresponding colors (strong fluorescence intensity) under 365nm excitation, removing illumination, enabling the fluorescence intensity of the assembly system carrying fluorescent dye molecules to be weakened along with the transition of the nano particles, and enabling no fluorescence with corresponding colors to be emitted even under 365nm excitation. In the self-assembly system, the spherical nano particles formed by assembling anions formed by isomerization of the photoacid molecules and polyethyleneimine cations show stronger electronegativity, so that in the spherical nano particles, the charge transfer effect of the fluorescent dye is smaller, and the spherical nano particles form better hydrophobic environment due to assembly, so that the spherical nano particles show stronger fluorescent intensity. In square nano particles, the photo-acid isomerism molecules are gradually recovered, the system is converted into neutrality, the charge transfer effect of the system is stronger, the fluorescent dye is subjected to aggregation-induced quenching, and fluorescence is quenched. In fluorescent systems, charge transfer (negatively charged systems are weaker than the charge transfer effects of positively charged and electrically neutral systems) typically results in fluorescence aggregation-induced quenching or fluorescence redshift.
Wherein the fluorescent dye is composed of blue fluorescent dye and/or green fluorescent dye and/or red fluorescent dye.
The preparation method of the fluorescent ink based on the light-operated nano particles comprises the following steps:
(1) Preparing a light-operated nanoparticle precursor solution: dissolving a photoacid compound in acidic water, and adding a polyethyleneimine aqueous solution into the water after ultrasonic dissolution to obtain a light-controlled nanoparticle precursor solution; at this time, the photoacid compound and the polyethyleneimine in the solution are in a free state;
(2) Adding a solution containing blue and/or red and/or green fluorescent dyes into the precursor solution in the step (1), and obtaining fluorescent ink with corresponding color after light irradiation of 420+/-10 nm; after illumination, the photoacid compound and polyethyleneimine in the precursor solution are polymerized to assemble spherical nanoparticles, and fluorescent dye molecules are wrapped in the spherical nanoparticles.
Wherein, in the step (1), the acidic water is that dilute hydrochloric acid is added into the water to enable the pH value of the water to be 5-6, if the pH value of the initial deionized water is 8, 1 microliter of 1mM dilute hydrochloric acid is added into 10mL of water to enable the pH value of the water to be adjusted to be 5-6. The structure of the photoacid molecule can be broken under the alkaline condition, so that the photoisomerization property is lost, and the isomerism performance of the photoacid molecule is better only when the pH value of the solution is 5-6.
Wherein in the step (1), the concentration of the polyethyleneimine in the polyethyleneimine aqueous solution is 1mg/mL, and the weight average molecular weight of the polyethyleneimine is 10000. Only when the molecular weight of the polyethyleneimine is 10000, the photoacid and the polyethyleneimine have better assembly effect.
Wherein in the step (1), the concentration of the polyethyleneimine in the precursor solution is 5 mug/mL; the photoacid concentration was 0.225mM.
The optimal assembly concentration of photoacid compound was determined to be 0.225mM by increasing the photoacid concentration from 0.05mM to 0.325mM, and by determining the critical aggregation concentration CAC, found by linear fitting through ultraviolet transmission variation at 650nm, to be 0.1521mM after light irradiation at 420 nm. The concentration of the photoacid compound was fixed at 0.225mM, the concentration of the polyethylenimine was varied from 0.5. Mu.g/mL to 7.5. Mu.g/mL in steps of 0.5. Mu.g/mL, and after irradiation with light at 420nm, an optimum assembly concentration of polyethylenimine of 5. Mu.g/mL was obtained by variation of UV transmission at 650 nm.
In the step (2), the blue fluorescent dye solution is a DMSO (dimethyl sulfoxide) solution of scoparone, only the DMSO solution of scoparone is added into the current precursor solution, and after light irradiation of 420+/-10 nm, blue fluorescent ink is obtained, and the emission wavelength is 425nm; the concentration of the scoparone in the mixed solution is 0.001mM; the red fluorescent dye solution is sulforhodamine 101 water solution, only the sulforhodamine 101 water solution is added into the precursor solution, and after 420+/-10 nm light irradiation, the red fluorescent ink is obtained, and the emission wavelength is 606nm; the concentration of sulforhodamine 101 in the mixed solution is 0.006mM; the green fluorescent dye solution is a DMSO solution of 5 (6) -carboxyl fluorescein diacetate, only the DMSO solution of 5 (6) -carboxyl fluorescein diacetate is added into the precursor solution, and after light irradiation of 420+/-10 nm, the green fluorescent ink is obtained, and the emission wavelength is 520nm; the concentration of 5 (6) -carboxyfluorescein diacetate in the mixture was 0.01mM.
In the step (2), a blue fluorescent dye solution and a red fluorescent dye solution are added into a precursor solution at the same time, or a green fluorescent dye solution and a red fluorescent dye solution are added into the precursor solution at the same time, or a blue fluorescent dye solution and a green fluorescent dye solution are added into the precursor solution at the same time, and fluorescent ink with a required color is obtained after light irradiation of 420+/-10 nm by adjusting the mixing proportion of the fluorescent dye solutions. The method comprises the following steps: simultaneously adding a DMSO solution of scoparone and a sulforhodamine 101 aqueous solution into the precursor solution to prepare a solution with the scoparone concentration of 0.0003mM and the sulforhodamine 101 concentration of 0.006mM, and irradiating with 420nm light for 10 minutes to obtain pink fluorescent ink; simultaneously adding a DMSO solution of 5 (6) -carboxyfluorescein diacetate and an aqueous solution of sulforhodamine 101 into the precursor solution to prepare a solution with the concentration of 5 (6) -carboxyfluorescein diacetate of 0.02mM and the concentration of sulforhodamine 101 of 0.003mM, and irradiating with 420nm light for 10 minutes to obtain yellow fluorescent ink; simultaneously adding a DMSO solution of scoparone and a DMSO solution of 5 (6) -carboxyl fluorescein diacetate into the precursor solution to prepare a solution with the concentration of scoparone being 0.0001mM and the concentration of 5 (6) -carboxyl fluorescein diacetate being 0.03mM, and irradiating with light at 420nm for 10 minutes to obtain cyan fluorescent ink; simultaneously adding a DMSO solution of scoparone, a DMSO solution of 5 (6) -carboxyl fluorescein diacetate and an aqueous solution of sulforhodamine 101 into the precursor solution to prepare a solution with the concentration of scoparone of 0.0002mM, the concentration of 5 (6) -carboxyl fluorescein diacetate of 0.025mM and the concentration of sulforhodamine 101 of 0.004mM, and irradiating with 420nm light for 10 minutes to obtain the white fluorescent ink.
The beneficial effects are that: (1) The invention can obtain fluorescent ink with various colors, the light-operated nano particles are obtained by self-assembling the photoacid molecules and the polyethyleneimine molecules, at least one fluorescent dye molecule of blue, green and red is wrapped in the nano particles, and the fluorescent ink with various colors can be prepared by arbitrarily mixing the blue, green and red colors; (2) The fluorescent ink has double excitation response, firstly, the fluorescent ink can trigger color development after being irradiated by 420nm light, and then, the color can be seen after being excited by 365nm ultraviolet light, so that the safety anti-counterfeiting grade can be obviously improved when the fluorescent ink is applied to the anti-counterfeiting field; (3) The fluorescent ink provided by the invention can excite color development when color development is needed, and can not perform fluorescent color development when color development is not needed.
Drawings
FIG. 1 is a graph of UV transtitration with immobilized polyethylenimine concentration at 5 μg/mL, photoacid concentration from 0.05mM to 0.325mM, increasing step size of 0.025 mM;
FIG. 2 is a graph of increasing UV transtitration of immobilized photoacid concentration of 0.225mM, polyethyleneimine concentration from 0.5 μg/mL to 7.5 μg/mL, with a step size of 0.5 μg/mL;
FIG. 3 is a transmission electron microscope image of spherical nanoparticles;
FIG. 4 is a square nanoparticle transmission electron microscope image;
FIG. 5 shows the change in fluorescence intensity under 340nm excitation before and after illumination with 0.001mM scoparone at 420 nm;
FIG. 6 shows the change in fluorescence intensity at 440nm excitation before and after irradiation with light at 420nm for 0.01mM5 (6) -carboxyfluorescein diacetate;
FIG. 7 shows the change in fluorescence intensity under 585nm excitation before and after 0.005mM sulforhodamine 101, 420nm light irradiation;
FIG. 8 is a graph of seven fluorescent inks of cyan i (0.0001 mM scoparone, 0.03mM 5 (6) -carboxyfluorescein diacetate), pink ii (0.0003 mM scoparone, 0.006mM sulforhodamine 101), yellow iii (0.02 mM5 (6) -carboxyfluorescein diacetate, 0.003mM sulforhodamine 101), white iv (0.0002 mM scoparone, 0.025mM 5 (6) -carboxyfluorescein diacetate, 0.004mM sulforhodamine 101), blue v (0.001 mM scoparone), green vi (0.01 mM5 (6) -carboxyfluorescein diacetate), red vii (0.006 mM sulforhodamine 101), corresponding color coordinate points on the CIE chromaticity diagram after 420nm excitation;
FIG. 9 is a photograph showing actual fluorescence after excitation of three fluorescent inks of blue, green and red;
FIG. 10 is a photograph of actual fluorescence after excitation of four fluorescent inks of yellow-pink and white;
FIG. 11 is a photograph of a 96-well plate filled with different fluorescent inks according to a design under natural light;
FIG. 12 is a photograph of a 96-well plate filled with different fluorescent inks according to a design pattern under 365nm light excitation;
FIG. 13 is a photograph of a 96-well plate filled with different fluorescent inks according to a design pattern under 365nm light excitation after 420nm light irradiation; s is the site filled with blue fluorescent ink, E is the site filled with red fluorescent ink, and U is the site filled with green fluorescent ink.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The fluorescent ink based on the light-operated nano particles is an aqueous solution containing a photoacid compound, polyethylenimine and fluorescent dye; and (3) polymerizing the photoacid compound and the polyethyleneimine to assemble spherical nano particles under the light irradiation of 420nm, wrapping fluorescent dye molecules in the spherical nano particles, removing the light irradiation, placing the solution in a dark place to avoid light, and reversely changing the nano particle structure assembled by the photoacid compound and the polyethyleneimine.
The preparation method of the fluorescent ink based on the light-operated nano particles specifically comprises the following steps:
(1) Preparing a light-operated nanoparticle precursor solution: dissolving a photoacid compound in water with a pH value of 5-6, fully dissolving by ultrasonic, and then adding a polyethyleneimine (polyethyleneimine weight average molecular weight of about 10000) aqueous solution with a polyethyleneimine concentration of 1mg/mL into the water to obtain a light-operated nanoparticle precursor solution; in the precursor solution, the concentration of the photoacid compound was 0.225mM and the concentration of the polyethyleneimine was 5. Mu.g/mL.
Irradiating for 10 minutes under 420nm light under the corresponding assembly concentration of photoacid compound and polyethyleneimine to obtain spherical nano particles with the particle size of about 300 nm; placing in dark place for 20 min, and converting spherical nanoparticles into square nanoparticles with particle diameter of about 600nm;
the photoisomerization structural formula of the photoacid molecule is as follows:
the structural formula of the polyethyleneimine is as follows:
preparing blue fluorescent ink: adding a DMSO solution of scoparone into the precursor solution in the step (1) to obtain a mixed solution with the scoparone concentration of 0.001mM, and irradiating with 420nm light for 10 minutes to obtain blue fluorescent ink, wherein the maximum emission wavelength of the blue fluorescent ink is 425nm, the fluorescence intensity is 114 times enhanced before and after the light irradiation, and the coordinate position of the blue fluorescent color on a CIE chart is (0.156,0.0707) as shown in figure 5.
Preparing green fluorescent ink: and (3) adding a DMSO solution of 5 (6) -carboxyfluorescein diacetate into the precursor solution in the step (1) to obtain a mixed solution with the concentration of 5 (6) -carboxyfluorescein diacetate of 0.01mM, and irradiating with light at 420nm for 10 minutes to obtain green fluorescent ink, wherein the maximum emission wavelength of the green fluorescent ink is 520nm, the fluorescence intensity is 358 times enhanced before and after the light irradiation, and the coordinate position of the green fluorescent color on a CIE chart is (0.2949,0.6153) as shown in the figure 6.
Preparing red fluorescent ink: adding sulforhodamine 101 aqueous solution into the precursor solution in the step (1) to obtain mixed solution with the concentration of the sulforhodamine 101 of 0.006mM, and irradiating with 420nm light for 10 minutes to obtain red fluorescent ink, wherein the maximum emission wavelength of the red fluorescent ink is 606nm, the fluorescence intensity is enhanced by 4 times before and after the light irradiation, and the coordinate position of the red fluorescent color on a CIE chart is (0.6675,0.3322) as shown in figure 7. The light-operated nano particles have good reversible regulation and control effects on fluorescence of the solution before and after light irradiation after being loaded with fluorescent dye.
Preparing pink fluorescent ink: and (3) simultaneously adding a DMSO solution of scoparone and a sulforhodamine 101 aqueous solution into the precursor solution in the step (1) to obtain a mixed solution (the DMSO solvent content in the mixed solution is 0.5 percent, the system taking water as a fluorescent ink solvent is not influenced by the doping of a small amount of DMSO, the assembly process is basically not influenced by the DMSO content) with the concentration of scoparone of 0.0003mM and the concentration of sulforhodamine 101 of 0.006mM, and irradiating with 420nm light for 10 minutes to obtain the pink fluorescent ink.
Preparing yellow fluorescent ink: and (3) simultaneously adding a DMSO solution of 5 (6) -carboxyl fluorescein diacetate and an aqueous solution of sulforhodamine 101 into the precursor solution in the step (1) to obtain a mixed solution with the concentration of the 5 (6) -carboxyl fluorescein diacetate of 0.02mM and the concentration of the sulforhodamine 101 of 0.003mM, and irradiating with 420nm light for 10 minutes to obtain yellow fluorescent ink.
Preparing cyan fluorescent ink: and (3) simultaneously adding a DMSO solution of scoparone and a DMSO solution of 5 (6) -carboxyfluorescein diacetate into the precursor solution in the step (1) to obtain a mixed solution with the scoparone concentration of 0.0001mM and the 5 (6) -carboxyfluorescein diacetate concentration of 0.03mM, and irradiating with 420nm light for 10 minutes to obtain the cyan fluorescent ink.
Preparing white fluorescent ink: and (3) simultaneously adding a DMSO solution of scoparone, a DMSO solution of 5 (6) -carboxyfluorescein diacetate and an aqueous solution of sulforhodamine 101 into the precursor solution in the step (1) to obtain a mixed solution of scoparone with the concentration of 0.0002mM, 5 (6) -carboxyfluorescein diacetate with the concentration of 0.025mM and sulforhodamine 101 with the concentration of 0.004mM, and irradiating with 420nm light for 10 minutes to obtain the white fluorescent ink.
Table 1 shows three kinds of fluorescent dyes of blue, green and red, which are used as three primary colors, are mixed orthogonally, added into the precursor liquid of the step (1), and irradiated by 420nm light for 10 minutes, so as to obtain fluorescent ink with different colors:
the traditional fluorescent encryption mode is that the color is not developed under natural light and is developed under ultraviolet light. As can be seen from comparison of FIGS. 11-13, the fluorescent ink of the present invention has more than one encryption means by 420nm light irradiation, does not develop color under natural light before 420nm light irradiation (FIG. 11), does not develop color even under 365nm ultraviolet light (FIG. 12), does not see the encryption content, and can show a preset pattern only after 420nm light irradiation as shown in FIG. 13, thereby completely showing the double encryption process. Therefore, the fluorescent ink does not develop color under ultraviolet light excitation when not irradiated by 420nm light, and the fluorescent ink shows pre-designed fluorescent color under ultraviolet light excitation after irradiated by 420nm light, so that the fluorescent ink has double anti-counterfeiting effects of light-operated assembly and fluorescence excitation, and has a self-erasing function after irradiated by 420nm light is removed, so that the fluorescent ink has wide application prospects in the aspects of information encryption and anti-counterfeiting identification.
Claims (8)
1. The multicolor fluorescent ink based on the light-operated nano particles is characterized in that the fluorescent ink is an aqueous solution containing a photoacid compound, polyethylenimine and a fluorescent dye; under the light irradiation of 420+/-10 nm, the photoacid compound and the polyethyleneimine are polymerized to form spherical nano particles, fluorescent dye molecules are wrapped in the spherical nano particles, after the light irradiation is removed, the solution is placed in a dark place to avoid light, and the nano particle structure formed by the photoacid compound and the polyethyleneimine is reversely changed;
wherein the chemical structural formula of the photoacid compound is as follows:
2. the optically controlled nanoparticle-based multicolor fluorescent ink of claim 1, wherein: the fluorescent dye is composed of a blue fluorescent dye and/or a green fluorescent dye and/or a red fluorescent dye.
3. The method for preparing multicolor fluorescent ink based on light-operated nano particles as set forth in claim 1, comprising the steps of:
(1) Dissolving a photoacid compound in acidic water, and adding a polyethyleneimine aqueous solution into the water after ultrasonic dissolution to obtain a light-controlled nanoparticle precursor solution; at this time, the photoacid compound and the polyethyleneimine in the solution are in a free state;
(2) Adding a solution containing blue and/or red and/or green fluorescent dyes into the precursor solution in the step (1), and obtaining fluorescent ink with corresponding color after light irradiation of 420+/-10 nm; after illumination, the photoacid compound and polyethyleneimine in the precursor solution are polymerized to assemble spherical nanoparticles, and fluorescent dye molecules are wrapped in the spherical nanoparticles.
4. The method for preparing the multicolor fluorescent ink based on the light-operated nano particles according to claim 3, which is characterized in that: in the step (1), the pH value of the acidic water is 5-6.
5. The method for preparing the multicolor fluorescent ink based on the light-operated nano particles according to claim 3, which is characterized in that: in the step (1), the concentration of the polyethyleneimine in the polyethyleneimine aqueous solution is 1mg/mL, and the weight average molecular weight of the polyethyleneimine is 10000.
6. The method for preparing the multicolor fluorescent ink based on the light-operated nano particles according to claim 3, which is characterized in that: in the step (1), the concentration of the polyethyleneimine in the precursor solution is 5-5.5 mug/mL; the concentration of the photoacid compound is 0.225 to 0.226mM.
7. The method for preparing the multicolor fluorescent ink based on the light-operated nano particles according to claim 3, which is characterized in that: in the step (2), the blue fluorescent dye solution is a DMSO solution of scoparone, and only the DMSO solution of scoparone is added into the precursor solution, and after light irradiation of 420+/-10 nm, the blue fluorescent ink is obtained; the red fluorescent dye solution is sulforhodamine 101 water solution, only the sulforhodamine 101 water solution is added into the precursor solution, and after light irradiation of 420+/-10 nm, red fluorescent ink is obtained; the green fluorescent dye solution is a DMSO solution of 5 (6) -carboxyl fluorescein diacetate, only the DMSO solution of 5 (6) -carboxyl fluorescein diacetate is added into the precursor solution, and after light irradiation of 420+/-10 nm, the green fluorescent ink is obtained.
8. The method for preparing multicolor fluorescent ink based on light-operated nano particles according to claim 7, wherein: in the step (2), a blue fluorescent dye solution and a red fluorescent dye solution are added into a precursor solution at the same time, or a green fluorescent dye solution and a red fluorescent dye solution are added into the precursor solution at the same time, or a blue fluorescent dye solution and a green fluorescent dye solution are added into the precursor solution at the same time, and fluorescent ink with a required color is obtained after light irradiation of 420+/-10 nm through adjustment of the mixing proportion of the fluorescent dye solutions.
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| CN104031477A (en) * | 2014-06-25 | 2014-09-10 | 吉林大学 | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles |
| CN112175449A (en) * | 2020-11-16 | 2021-01-05 | 武汉理工大学 | Super-stable printable aqueous fluorescent anti-counterfeiting ink and preparation method thereof |
| CN113755057A (en) * | 2021-07-30 | 2021-12-07 | 哈尔滨工业大学（深圳） | Water-based fluorescent ink, preparation method thereof and application thereof in full-color printing and encryption anti-counterfeiting |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031477A (en) * | 2014-06-25 | 2014-09-10 | 吉林大学 | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles |
| CN112175449A (en) * | 2020-11-16 | 2021-01-05 | 武汉理工大学 | Super-stable printable aqueous fluorescent anti-counterfeiting ink and preparation method thereof |
| CN113755057A (en) * | 2021-07-30 | 2021-12-07 | 哈尔滨工业大学（深圳） | Water-based fluorescent ink, preparation method thereof and application thereof in full-color printing and encryption anti-counterfeiting |
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