CN111892843A - Preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink - Google Patents
Preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink Download PDFInfo
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Abstract
The invention discloses a preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink, belonging to the technical field of nano optical anti-counterfeiting, and the method comprises the following steps: firstly, preparing nanoparticles with red-green-blue orthogonal up-conversion luminescence by a layer-by-layer wrapping method by using a full-automatic nano synthesizer, then carrying out surface treatment on the obtained nanoparticles to obtain water-soluble nanoparticles, finally adding the water-soluble nanoparticles into an acid-base indicator according to a certain proportion, and carrying out ultrasonic dispersion uniformly to obtain the safety ink. The security ink prepared by the method can obtain anti-counterfeiting patterns through printing, stamping, ink-jet printing, handwriting and other modes, and the patterns obtained by the security ink have the characteristics of tricolor fluorescence display, good pH stimulation responsiveness, good stability and the like, and can be used for multi-level anti-counterfeiting application.
Description
Technical Field
The invention relates to a preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink, and belongs to the technical field of nano optical anti-counterfeiting.
Background
Information security has become an important issue in modern society, and thus, anti-counterfeiting technology plays an increasingly important role in political, economic and military fields as well as in our daily lives. Statistically, governments and businesses around the world have spent tens of millions of dollars for the development of information protection and anti-counterfeiting technologies over the past several decades. Various anti-counterfeiting technologies, including fluorescence anti-counterfeiting, nuclear track anti-counterfeiting, laser holographic anti-counterfeiting, magnetic anti-counterfeiting and the like, have been widely applied to currency, labels and important documents. Among them, the security ink based on the fluorescence anti-counterfeiting technology has been widely used in the fields of information storage, security anti-counterfeiting and the like because of its advantages of good stability, convenient printing, low cost, good concealment and the like. The traditional fluorescent anti-counterfeiting ink is usually based on a single-stage anti-counterfeiting technology, and although ink marks cannot be seen under natural light, the ink marks can be displayed under the excitation of ultraviolet light or near infrared light. The fluorescent anti-counterfeiting ink based on the single-stage anti-counterfeiting technology can be replaced by a luminescent material with similar emission characteristics, so that the generated anti-counterfeiting pattern lacks effective protection on information, and is not ideal in information protection, low in anti-counterfeiting performance and easy to counterfeit. Therefore, the development of more concealed and safer advanced anti-counterfeiting technology is important for striking various renovation activities.
Disclosure of Invention
The invention aims to provide a preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink to promote the development of a higher-grade anti-counterfeiting technology.
The invention is realized by the following technical scheme:
a preparation method of red-green-blue three-primary-color orthogonal up-conversion fluorescent safety ink comprises the steps of firstly preparing nanoparticles with red-green-blue three-primary-color orthogonal up-conversion luminescence by a layer-by-layer wrapping method by using a full-automatic nanometer synthesizer, then carrying out surface modification on the nanoparticles to obtain water-soluble nanoparticles with good dispersibility, finally adding a water-soluble nanoparticle solution into an acid-base indicator, and carrying out ultrasonic dispersion to obtain the red-green-blue three-primary-color orthogonal up-conversion fluorescent safety ink.
Preferably, the volume ratio of the water-soluble nanoparticle solution to the acid-base indicator is 1:1 to 2.
Preferably, the preparation method of the nanoparticle with red, green and blue three primary colors orthogonal up-conversion luminescence specifically comprises the following steps: firstly preparing NaYF4Yb/Tm core nanoparticles, and then forming NaYF by using the core nanoparticles as seed crystals through a method of inducing crystal epitaxial growth shell4:Yb/Tm@NaYF4One layer of core-shell structure nano particles are formed, and then the formed one layer of core-shell structure nano particles are used as seed crystals to induce epitaxial growth of NaYF4Er/Ho layer to form NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho double-layer core-shell structure nano-particles; taking the nano particles prepared in the previous step as seed crystals, preparing a third layer, a fourth layer and a fifth layer by inducing a crystal epitaxial growth shell layer mode and the like, and finally preparing the NaYF with a one-core five-shell structure4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4Nd core-shell structured nanoparticles.
Preferably, the NaYF4The preparation method of the Yb/Tm core nano-particle specifically comprises the step of adding 0.4mmol of Y (CH) in the total amount according to a preset proportion3COO)3(69.5％)、Yb(CH3COO)3(30%) and Tm (CH)3COO)3(0.5%) of an aqueous solutionAdding 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and low-boiling solvent molecules to form an oleic acid complex precursor; the resulting mixture was then cooled to room temperature and 4mL NH was added4F (0.4moL/L) and 2mLNaOH (0.5moL/L) in methanol, heating to 50 ℃, continuously stirring for 30 minutes, heating to 100 ℃, keeping for 10 minutes under vacuum conditions to remove methanol, and then heating to 290 ℃ under the protection of inert gas to react for 90 minutes; after the reaction is finished, cooling to room temperature, centrifugally separating the prepared core nanoparticles by precipitation, repeatedly washing the core nanoparticles with cyclohexane and ethanol for three times, and finally dispersing the product in cyclohexane for further shell growth.
Preferably, the NaYF4:Yb/Tm@NaYF4A preparation method of a layer of core-shell structure nano-particles comprises the step of mixing 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4Yb/Tm core nanoparticle (. about.0.4 mmol) and then 4mL NH was added4Keeping and stirring the methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) for 30 minutes, then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; and (3) carrying out centrifugal separation and precipitation to prepare a layer of core-shell structure nanoparticles, repeatedly washing the core-shell structure nanoparticles for three times by using cyclohexane and ethanol, and finally dispersing the product in the cyclohexane for further shell growth.
Preferably, the NaYF4:Yb/Tm@NaYF4@NaYF4A process for preparing Er/Ho double-layer core-shell nanoparticles, specifically 0.4mmol of Y (CH)3COO)3(90％)、Er(CH3COO)3(5%) and Ho (CH)3COO)3(5%) the aqueous solution was added to 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60 minutes to remove water and low boiling solvent molecules, forming an oleic acid complex precursor. Then cooling to roomAdding the prepared NaYF solution at a warm temperature4:Yb/Tm@NaYF4One layer of core-shell structured nanoparticles (. about.0.4 mmol) and then 4mL NH was added4And keeping stirring for 30 minutes by using a methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L), then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished. And (3) carrying out centrifugal separation and precipitation on the prepared double-layer core-shell structure nanoparticles, repeatedly washing the double-layer core-shell structure nanoparticles for three times by using cyclohexane and ethanol, and finally dispersing the product in the cyclohexane for further shell layer growth.
Preferably, the NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4A preparation method of three-layer core-shell structure nanoparticles is provided, and specifically 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho double-layer core-shell structured nanoparticles (0.4 mmol) and then 4mL NH was added4Keeping and stirring the methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) for 30 minutes, then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; and (3) carrying out centrifugal separation and precipitation on the prepared three-layer core-shell structure nano particles, repeatedly washing the three-layer core-shell structure nano particles by using cyclohexane and ethanol for three times, and finally dispersing the product in the cyclohexane for further shell layer growth.
Preferably, the NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4A preparation method of Nd/Yb/Er four-layer core-shell structure nano-particles, in particular to 0.4mmol of Y (CH)3COO)3(77.5％)、Nd(CH3COO)3(0.5％)、Yb(CH3COO)3(20％)、Nd(CH3COO)3(2%) aqueous solution was added to 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60Removing water and low-boiling solvent molecules in minutes to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4Three layers of core-shell structured nanoparticles (. about.0.4 mmol) and then 4mL NH was added4Keeping and stirring the methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) for 30 minutes, then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; and (3) carrying out centrifugal separation and precipitation on the prepared four-layer core-shell structure nano particles, repeatedly washing the four-layer core-shell structure nano particles for three times by using cyclohexane and ethanol, and finally dispersing the product in the cyclohexane for further shell layer growth.
Preferably, the NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4A preparation method of Nd five-layer core-shell structured nano particles, in particular to 0.4mmol of Y (CH)3COO)3(80％)、Nd(CH3COO)3(20%) of the aqueous solution was added to 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60 minutes to remove water and low-boiling solvent molecules, forming an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4Nd/Yb/Er four-layer core-shell structured nanoparticles (. about.0.4 mmol) and subsequently 4mL NH was added4Keeping and stirring the methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) for 30 minutes, then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; the five-layer core-shell structure nano-particles prepared by centrifugal separation and precipitation are repeatedly washed three times by using cyclohexane and ethanol, and finally the product is dispersed in the cyclohexane for characterization.
Preferably, the NaYF4The Yb/Tm nuclear nano particle has the size of 25nm and generates blue light fluorescence under the excitation of 980nm near infrared light; the NaYF4The thickness of the first shell layer is 4.5nm,for preventing unnecessary energy transfer and cross relaxation between the blue light emitting core and the red light emitting layer, so that the blue light emission and the red light emission do not interfere with each other; the NaYF4The thickness of the second Er/Ho shell layer is 4.5nm, and the second Er/Ho shell layer is used for generating red fluorescence under the excitation of 1560nm near infrared light; the NaYF4The thickness of the third shell layer is 6nm, and the third shell layer is used for preventing unnecessary energy transfer and cross relaxation between the red light emitting layer and the green light emitting layer, so that red light emission and green light emission are not interfered with each other; the NaYF4The thickness of the fourth Nd/Yb/Er shell layer is 5nm, and the fourth Nd/Yb/Er shell layer is used for generating green fluorescence under the excitation of near infrared light of 808 nm; the NaYF4The thickness of the Nd fifth shell layer is 3nm and is used for absorbing the energy of near infrared light with the wavelength of 808 nm.
Preferably, the nanoparticles are surface-modified by the following specific method: the oleic acid ligand on the surface of the nano-particle is protonated by dilute hydrochloric acid, so that the oleic acid ligand on the surface is converted into oleic acid molecules to fall off from the surface, and the three-primary-color orthogonal luminescent five-layer core-shell structure nano-particle which is hydrophilic and is not modified by the surface ligand is formed.
Preferably, the acid-base indicator is one of p-nitrophenol, m-nitrophenol, phenolphthalein, thymolphthalein, o-cresolphthalein, quinoline blue, quinoline yellow or s-trinitrobenzene.
Compared with the prior fluorescent anti-counterfeiting technology, the invention has the advantages that:
(1) the safety ink prepared by the method has up-conversion luminescence characteristics, and ink marks can be displayed by near infrared light excitation. Compared with the common fluorescent anti-counterfeiting ink, the fluorescent anti-counterfeiting ink avoids background fluorescence generated by a fluorescent whitening agent in paper under the excitation of ultraviolet light, thereby avoiding background fluorescence interference caused by down-conversion fluorescence to the anti-counterfeiting ink.
(2) Under the excitation of near infrared light with three different wavelengths (1560nm, 808nm and 980nm), the safety ink prepared by the method can respectively generate fluorescence emission of three primary colors of red, green and blue. The anti-counterfeiting technology based on the triple excitation response tricolor fluorescence obviously improves the grade of safety anti-counterfeiting and increases the simulated technical difficulty.
(3) The safety ink prepared by the method has the characteristic of pH stimulation response. Under natural light, the ink is blue at pH >10.5 and colorless at pH < 10.5. The safety ink based on pH response has the characteristics of convenient storage, easy identification and irreplaceability, thereby further improving the grade of safety and anti-counterfeiting.
(4) By adjusting the pH value, the fading time of the safe ink under natural light can be accurately regulated and controlled. The regulation and control of the fading time of the safety ink are very important for timely hiding the identified anti-counterfeiting information, and the information can be effectively prevented from being leaked in the identification process.
Drawings
FIG. 1: the photo of the fluorescence safety ink is converted on the red, green and blue three primary colors in an orthogonal mode. The safe ink is uniformly dispersed and is colorless and transparent.
FIG. 2: the structure of three-primary-color orthogonal light-emitting five-layer core-shell structure nano-particles. Under the excitation of 1560nm, 808nm and 980nm different wavelengths, the nano-particle cyclohexane solution respectively emits red, green and blue up-conversion fluorescence.
FIG. 3: photographs of the trichromatic upconversion fluorescent security ink after addition of strongly basic NaOH solution (pH >10.5) show that the security ink is blue at pH > 10.5.
FIG. 4: the color-changed security ink of fig. 3 was returned to its original colorless state after addition of the strong acid HCl solution (pH <1), indicating that the ink was colorless under acidic or neutral conditions and that repeated transitions between blue and colorless states were possible.
Detailed Description
The following embodiments are only used for illustrating the technical solutions of the present invention more clearly, and therefore, the following embodiments are only used as examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1
The preparation method of the tricolor orthogonal light-emitting five-layer core-shell structure nano-particles comprises the following specific steps:
(1)NaYF4synthesis of Yb/Tm core nanoparticles. Taking a 50mL two-neck round-bottom flask as a reaction vessel, adding Y (CH) in a predetermined proportion and in a total amount of 0.4mmol3COO)3(69.5％)、Yb(CH3COO)3(30%) and Tm (CH)3COO)3(0.5%) of an aqueous solution was added 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60 minutes to remove water and low boiling solvent molecules, forming an oleic acid complex precursor. After the resulting mixture was cooled to room temperature, 4mL of NH was added4F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol are heated to 50 ℃ and stirred continuously for 30 minutes, then the temperature is raised to 100 ℃ and kept for 10 minutes under vacuum condition to remove the methanol, and then the temperature is raised to 290 ℃ under the protection of inert gas for 90 minutes. After the reaction is finished, cooling to room temperature, carrying out centrifugal separation on the nano particles prepared by precipitation, repeatedly washing the nano particles by using cyclohexane and ethanol for several times, and finally dispersing the product in the cyclohexane for further shell growth.
(2)NaYF4:Yb/Tm@NaYF4And (3) synthesizing core-shell structure nanoparticles of the core @ shell layer 1. The core-shell nano-particles are prepared by a method of epitaxial shell growth. 0.4mmol of Y (CH)3COO)3The aqueous solution was added to 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60 minutes to form an oleic acid complex Y-OA shell precursor. Then cooled to 50 ℃ and added with the prepared core nanoparticles (-0.4 mmol) and then 4mL NH4And keeping stirring for 30 minutes by using a methanol solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L), then heating to 100 ℃, keeping for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after removal of the cyclohexane and the methanol, reacting for 90 minutes, and cooling to room temperature after the reaction is finished. The nanoparticles prepared were precipitated by centrifugation, washed several times repeatedly with cyclohexane and ethanol and finally the product was dispersed in cyclohexane for further shell growth.
(3)NaYF4:Yb/Tm@NaYF4@NaYF4The synthesis of core-shell nano-particles of Er/Ho core @ shell 1@ shell 2. Similar to the preparation method of the core @ shell 1 nano-particles. Adding Y (CH) in a predetermined ratio in a total amount of 0.4mmol3COO)3(90％)、Er(CH3COO)3(5%) and Ho (CH)3COO)3(5%) aqueous solution is prepared into a precursor of a Y, Er, Ho-OA shell layer, the core-shell structure nano-particles prepared in the previous time are used as seed crystals, and then NaYF is induced and extended4Growing Er/Ho shell. And dispersing the prepared nano particles with the double-shell core-shell structure into a cyclohexane solution for further shell growth.
(4)NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4And (3) synthesizing core-shell structure nano particles of a core @ shell layer 1@ shell layer 2@ shell layer 3. Similar to the preparation method of the nano-particles with the core @ shell 1@ shell 2 structure. The total amount of Y (CH) was 0.4mmol3COO)3Preparing a precursor of a Y-OA shell layer from an aqueous solution, taking the double-layer core-shell structure nano particles prepared at the previous time as seed crystals, and then carrying out induced epitaxy on NaYF4And (5) growing a shell layer. And dispersing the prepared nano particles with the three-shell core-shell structure into a cyclohexane solution for further shell growth.
(5)NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4The synthesis of the core-shell structure nano-particles of Nd/Yb/Er core @ shell 1@ shell 2@ shell 3@ shell 4. The preparation method is similar to the preparation method of the nano-particles with the structure of the core @ shell 1@ shell 2@ shell 3. Adding Y (CH) in a predetermined ratio in a total amount of 0.4mmol3COO)3(77.5％)、Nd(CH3COO)3(0.5％)、Yb(CH3COO)3(20％)、Nd(CH3COO)3(2%) aqueous solution is prepared into a precursor of a Y, Nd, Yb, Er-OA shell layer, the three-layer core-shell structure nano-particles prepared in the previous time are used as seed crystals, and then the NaYF is induced and extended4Growing Nd/Yb/Er shell layer. And dispersing the prepared nano particles with the four-shell core-shell structure into a cyclohexane solution for further shell growth.
(6)NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/E@NaYF4The synthesis of the core-shell structure nano-particles of Nd core @ shell 1@ shell 2@ shell 3@ shell 4@ shell 5. The preparation method is similar to the preparation method of the nanoparticle with the structure of the core @ shell 1@ shell 2@ shell 3@ shell 4. Adding Y (CH) in a predetermined ratio in a total amount of 0.4mmol3COO)3(80％)、Nd(CH3COO)3(20%) aqueous solution is prepared into a precursor of a Y, Nd-OA shell layer, the four-layer core-shell structure nano-particles prepared in the previous time are used as seed crystals, and then the epitaxial growth of NaYF is induced4Growing Nd shell layer. Dispersing the prepared nanoparticles with the five-shell core-shell structure into a cyclohexane solution.
Example 2: and (3) preparing hydrophilic three-primary-color orthogonal luminescent five-layer core-shell structure nanoparticles.
Dispersing the three-primary-color orthogonal luminescent nano-particles wrapped by oleic acid into a mixed solution of 1ml of ethanol and 1ml of hydrochloric acid (2M), then centrifuging at the rotating speed of 16000r/min for 20min to remove oleic acid ligands on the surfaces of the nano-particles, washing the obtained nano-particles without the ligands on the surfaces twice by using ethanol, and finally dispersing in deionized water.
Example 3: and (3) preparing a thymolphthalein solution serving as an acid-base indicator. Weighing 0.1g thymolphthalein, dissolving in 100ml ethanol with volume fraction of 90%, and performing ultrasonic treatment to completely dissolve.
Example 4: and (3) preparation of the red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink.
Dispersing the prepared water-soluble five-layer core-shell structure nano-particle solution with the tricolor orthogonal luminescence into thymolphthalein solution at room temperature according to the volume ratio of 1: 1-2, and ultrasonically oscillating the obtained dispersion liquid for 30min to uniformly disperse the dispersion liquid to obtain the red-green-blue tricolor orthogonal up-conversion fluorescence safety ink.
By adjusting the pH value of the fluorescent safety ink converted in the three primary colors of red, green and blue, the time (fading time) required by the safety ink from writing to disappearance under natural light can be regulated and controlled, as shown in Table 1.
TABLE 1 time table required for the safety ink to disappear from writing under natural light
CLW: the ink is coloured but is written colourless
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink is characterized in that firstly, nanoparticles with red, green and blue three-primary-color orthogonal up-conversion luminescence are prepared by a layer-by-layer wrapping method by using a full-automatic nanometer synthesizer, then the nanoparticles are subjected to surface modification to obtain water-soluble nanoparticles with good dispersibility, and finally, a water-soluble nanoparticle solution is added into an acid-base indicator, and is subjected to uniform ultrasonic dispersion to obtain the red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink; the volume ratio of the water-soluble nano particle solution to the acid-base indicator is 1:1 to 2.
2. The preparation method of the red-green-blue three-primary-color orthogonal up-conversion fluorescent security ink as claimed in claim 1, wherein the preparation method of the nanoparticles having red-green-blue three-primary-color orthogonal up-conversion luminescence specifically comprises the following steps: firstly preparing NaYF4Yb/Tm core nanoparticles, and then forming NaYF by using the core nanoparticles as seed crystals through a method of inducing crystal epitaxial growth shell4:Yb/Tm@NaYF4One layer of core-shell structure nano particles are formed, and then the formed one layer of core-shell structure nano particles are used as seed crystals to induce epitaxial growth of NaYF4Er/Ho layer to form NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho double-layer core-shell structure nano-particles; taking the nano particles prepared in the previous step as seed crystals, and preparing a third layer of NaYF by inducing a crystal epitaxial growth shell layer and the like4And the fourth layer of NaYF4Nd/Yb/Er and fifth-layer NaYF4Nd, finally preparing the NaYF with a one-core five-shell structure4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4Nd core-shell structured nanoparticles.
3. The method for preparing red, green and blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 2, wherein the NaYF is prepared by a method of preparing the NaYF4The preparation method of the Yb/Tm core nano-particle is to add 69.5 percent of Y (CH) according to the predetermined proportion and the total amount of 0.4mmol3COO)330% of Yb (CH)3COO)3And a Tm (CH) of 0.5%3COO)3Adding 3mL of oleic acid and 7mL of octadecene into the aqueous solution, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; the mixture was then cooled to room temperature and NH was added4F and NaOH methanol solution are heated to 50 ℃ and continuously stirred for 30 minutes, then the temperature is raised to 100 ℃, the solution is kept for 10 minutes under the vacuum condition to remove the methanol, and then the solution is heated to 290 ℃ under the protection of inert gas to react for 90 minutes; after the reaction is finished, cooling to room temperature, centrifugally separating the prepared core nanoparticles by precipitation, repeatedly washing the core nanoparticles with cyclohexane and ethanol for three times, and finally dispersing the product in cyclohexane for further shell growth.
4. A RGB three primary colors orthogonal method as claimed in claim 3The preparation method of the up-conversion fluorescent safety ink is characterized in that the NaYF4:Yb/Tm@NaYF4A preparation method of a layer of core-shell structure nano-particles comprises the step of mixing 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4Yb/Tm core nanoparticles and subsequent addition of NH4Stirring the methanol solution of F and NaOH for 30 minutes, heating to 100 ℃, keeping the temperature for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the cyclohexane and the methanol are removed, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; and (3) carrying out centrifugal separation and precipitation to prepare a layer of core-shell structure nanoparticles, repeatedly washing the core-shell structure nanoparticles for three times by using cyclohexane and ethanol, and finally dispersing the product in the cyclohexane for further shell growth.
5. The method for preparing red, green and blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 4, wherein the NaYF is prepared by a method of preparing the NaYF4:Yb/Tm@NaYF4@NaYF4The preparation method of Er/Ho double-layer core-shell structure nano-particles specifically comprises the step of adding 90 percent of Y (CH) with the total amount of 0.4mmol according to a preset proportion3COO)35% Er (CH)3COO)3And 5% Ho (CH)3COO)3The aqueous solution was added to 3mL of oleic acid and 7mL of octadecene, and the resulting mixture was stirred at 150 ℃ for 60 minutes to remove water and low boiling solvent molecules, forming an oleic acid complex precursor. Then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4A layer of core-shell structured nanoparticles, and subsequently adding NH4And F and NaOH methanol solution are kept stirred for 30 minutes, then the temperature is raised to 100 ℃, the mixture is kept for 20 minutes under the vacuum condition to remove cyclohexane and methanol, the reaction temperature is heated to 290 ℃ after the cyclohexane and the methanol are removed, the mixture is reacted for 90 minutes, and the mixture is cooled to room temperature after the reaction is finished. The double-layer core-shell structure nano-particles prepared by centrifugal separation and precipitation are repeatedly washed for three times by using cyclohexane and ethanol, and finally the product is dispersed in the cyclohexaneIn an alkane for further shell growth.
6. The method for preparing red, green and blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 5, wherein the NaYF is prepared by a method of preparing the NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4A preparation method of three-layer core-shell structure nanoparticles is provided, and specifically 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho double-layer core-shell structure nano-particles and then adding NH4Stirring the methanol solution of F and NaOH for 30 minutes, heating to 100 ℃, keeping the temperature for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the cyclohexane and the methanol are removed, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; and (3) carrying out centrifugal separation and precipitation on the prepared three-layer core-shell structure nano particles, repeatedly washing the three-layer core-shell structure nano particles by using cyclohexane and ethanol for three times, and finally dispersing the product in the cyclohexane for further shell layer growth.
7. The method for preparing red, green and blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 1, wherein the NaYF is prepared by a method of preparing the NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4The preparation method of Nd/Yb/Er four-layer core-shell structure nano-particles specifically comprises the step of mixing 77.5 percent of Y (CH) with the total amount of 0.4mmol according to a preset proportion3COO)30.5% of Nd (CH)3COO)320% of Yb (CH)3COO)32% of Nd (CH)3COO)3Adding the aqueous solution into 3mL of oleic acid and 7mL of octadecene, and stirring the obtained mixture at 150 ℃ for 60 minutes to remove water and solvent molecules with low boiling point to form an oleic acid complex precursor; then cooling to room temperature and adding the prepared NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4Three-layer core-shell structureNanoparticles (. about.0.4 mmol) and subsequent addition of NH4Stirring the methanol solution of F and NaOH for 30 minutes, heating to 100 ℃, keeping the temperature for 20 minutes under a vacuum condition to remove cyclohexane and methanol, heating the reaction temperature to 290 ℃ after the cyclohexane and the methanol are removed, reacting for 90 minutes, and cooling to room temperature after the reaction is finished; the four-layer core-shell structure nano-particles are prepared by centrifugal separation and precipitation, cyclohexane and ethanol are used for repeatedly washing for three times, and finally, products are dispersed in the cyclohexane and used for NaYF4The growth of a fifth Nd shell layer is similar to the preparation method of the four-layer core-shell structure nano-particles; adding Y (CH) in a predetermined ratio in a total amount of 0.4mmol3COO)3(80％)、Nd(CH3COO)3(20%) aqueous solution is prepared into a precursor of a Y, Nd-OA shell layer, the four-layer core-shell structure nano-particles prepared in the previous time are used as seed crystals, and then the epitaxial growth of NaYF is induced4Growing Nd shell layer; dispersing the prepared nanoparticles with the five-shell core-shell structure into a cyclohexane solution.
8. The method for preparing red, green and blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 2, wherein the NaYF is prepared by a method of preparing the NaYF4The Yb/Tm nuclear nano particle has the size of 25nm and generates blue light fluorescence under the excitation of 980nm near infrared light; the NaYF4The thickness of the first shell layer is 4.5nm, and the first shell layer is used for preventing unnecessary energy transfer and cross relaxation between the blue light emitting core and the red light emitting layer, so that blue light emission and red light emission are not interfered with each other; the NaYF4The thickness of the second Er/Ho shell layer is 4.5nm, and the second Er/Ho shell layer is used for generating red fluorescence under the excitation of 1560nm near infrared light; the NaYF4The thickness of the third shell layer is 6nm, and the third shell layer is used for preventing unnecessary energy transfer and cross relaxation between the red light emitting layer and the green light emitting layer, so that red light emission and green light emission are not interfered with each other; the NaYF4The thickness of the fourth Nd/Yb/Er shell layer is 5nm, and the fourth Nd/Yb/Er shell layer is used for generating green fluorescence under the excitation of near infrared light of 808 nm; the NaYF4The thickness of the Nd fifth shell layer is 3nm and is used for absorbing the energy of near infrared light with the wavelength of 808 nm.
9. The preparation method of the red-green-blue three-primary-color orthogonal up-conversion fluorescent security ink according to claim 1, wherein the nanoparticles are subjected to surface modification by the following specific method: the oleic acid ligand on the surface of the nano-particle is protonated by dilute hydrochloric acid, so that the oleic acid ligand on the surface is converted into oleic acid molecules to fall off from the surface, and the three-primary-color orthogonal luminescent five-layer core-shell structure nano-particle which is hydrophilic and is not modified by the surface ligand is formed.
10. The method of claim 1, wherein the acid-base indicator is one of p-nitrophenol, m-nitrophenol, phenolphthalein, thymolphthalein, o-cresolphthalein, quinoline blue, quinoline yellow, or s-trinitrobenzene.
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