CN113201254A - Water-based nano anti-counterfeiting ink-jet ink and preparation method thereof - Google Patents

Abstract

The invention discloses aqueous nano anti-counterfeiting ink-jet ink and a preparation method thereof, wherein the aqueous nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 1-10 parts of fluorescent composite particles, 35-50 parts of aqueous resin, 0.1-0.5 part of sodium dodecyl benzene sulfonate, 0.01-0.03 part of ethylene glycol monomethyl ether, 1-10 parts of absolute ethyl alcohol and 50-80 parts of water; adding the fluorescent composite particles and the water-based resin into deionized water, adding absolute ethyl alcohol, magnetically stirring, cooling to room temperature, sequentially adding sodium dodecyl benzene sulfonate and ethylene glycol monomethyl ether, uniformly mixing, adjusting the pH until the pH is 9, and filtering to obtain the water-based nano anti-counterfeiting ink-jet ink; the primary material is core-shell structured nano particles prepared based on rare earth elements, and the quenching effect of surface defects such as a nano material dangling bond and a surface organic vibrating group on a fluorescent material can be effectively isolated through the core-shell structure, so that the luminous efficiency is improved.

Description

Water-based nano anti-counterfeiting ink-jet ink and preparation method thereof

Technical Field

The invention belongs to the technical field of printing ink, and particularly relates to water-based nano anti-counterfeiting ink-jet ink and a preparation method thereof.

Background

The ink is a uniform mixture composed of color bodies (such as pigments, dyes and the like), binders, filling materials, additives and the like; printing can be carried out, and drying is carried out on the printed body; is a colored pasty adhesive with certain fluidity. Thus, color (hue), body (rheology such as thickness, fluidity, etc.) and drying properties are the three most important properties of the ink. They are of various types, have different physical properties, and are thick and sticky; while some are quite rare. Some vegetable oil is used as a vehicle; some ink-jet inks use resin and solvent or water as a binder, but the existing ink-jet inks have no excellent anti-counterfeiting performance, cannot meet the anti-counterfeiting requirements of various industries, and influence the application range.

The chinese invention patent CN102639653B discloses an aqueous dispersion for aqueous printing ink and an aqueous printing ink containing the same, which can make the pigment dispersion state and storage stability of the aqueous printing ink excellent when used in the aqueous printing ink, and has excellent leveling property and ink permeability in printing quality, good color development and high gloss. Characterized in that the aqueous dispersion for aqueous printing ink is obtained by emulsion polymerization of a hydrophobic monomer (d) in a ratio in the presence of an alkali-soluble copolymer (A) obtained by radical copolymerization of a monomer (a) having an acid group, a monomer (b) containing an alkylene oxide chain represented by the following general formula (1), and a (meth) acrylic acid ester (c); this ratio is a mass ratio of the alkali-soluble copolymer (a) to the hydrophobic monomer (d), and is the alkali-soluble copolymer (a).

Disclosure of Invention

In order to overcome the technical problems, the invention provides aqueous nano anti-counterfeiting ink-jet ink and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

the water-based nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 1-10 parts of fluorescent composite particles, 35-50 parts of aqueous resin, 0.1-0.5 part of surfactant, 0.01-0.03 part of drier, 1-10 parts of absolute ethyl alcohol and 50-80 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65-75 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150-250r/min, cooling to room temperature after stirring, sequentially adding a surfactant and a drier, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

Further, the surfactant is any one of sodium dodecyl benzene sulfonate and tween-20, and the drier is any one of isopropanol and ethylene glycol monomethyl ether.

Further, the fluorescent composite particle is prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50-100r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding mixed liquor A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60-70 ℃ in the dropwise adding process, preserving heat at the temperature for 30min, then heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed liquor A to the solution precursor to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150 plus 200r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then putting the slurry into a dialysis bag of 500 plus 800Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is controlled to be 2: 3: 0.2-0.5.

Further, the mixed liquid A is formed by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.0-1.5 g: 2.0 g: 5 mL.

Cerium chloride hexahydrate, oleic acid and 1-octadecene are mixed in the step S1 to prepare a precursor solution, sodium hydroxide, ammonium fluoride and methanol are uniformly mixed to prepare a mixed solution A, the mixed solution A is dropwise added into the precursor solution to prepare a primary material, the primary material is core-shell structure nanoparticles prepared on the basis of rare earth elements, the core-shell structure can effectively isolate the quenching effect of surface defects such as a nano material dangling bond and a surface organic vibrating group on a fluorescent material, the luminous efficiency is improved, in the step S2, chitosan is used as a carbon source, glacial acetic acid is used as a condensing agent, ethylenediamine is used as a nitrogen doping agent, a fluorescent quantum is prepared by a microwave heating method, and then the fluorescent quantum is uniformly mixed, so that the prepared fluorescent composite particles have high-efficiency luminous efficiency, and the prepared ink has a fluorescent anti-counterfeiting effect.

Further, the aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 35-50 ℃, stirring at a constant speed of 120r/min at 100-, reacting for 2 hours at the temperature, washing for 3 times by using deionized water, standing for layering, collecting an organic phase, distilling under reduced pressure until no fraction appears, preparing a resin primary material, controlling the weight ratio of bisphenol A to epichlorohydrin to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate to be 3: 1, and the weight ratio of bisphenol A to 20% sodium hydroxide solution to be 3: 1.5-2;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution into a reaction kettle, reacting at the temperature of 120-150 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a dialysis bag with the molecular weight of 3500 for dialysis for 48 hours, collecting the dialysis external solution, evaporating by using a rotary evaporator, drying at the temperature of 90-100 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30-0.33mL, adding the nanoparticles into a resin primary material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the resin primary material.

In the step S1, bisphenol A and 1, 6-hexamethylene diisocyanate are mixed in epoxy chloropropane, the bisphenol A and the 1, 6-hexamethylene diisocyanate react to generate an intermediate, then the intermediate reacts with the epoxy chloropropane under the action of sodium hydroxide to generate a primary waterborne epoxy resin material, in the step S2, a nano particle is prepared by taking citric acid as a raw material, and the nano particle is blended, extruded and granulated to prepare the waterborne resin, so that the waterborne resin can be endowed with certain fluorescence performance.

A preparation method of water-based nano anti-counterfeiting ink-jet ink comprises the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65-75 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150-250r/min, cooling to room temperature after stirring, sequentially adding a surfactant and a drier, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

The invention has the beneficial effects that:

the invention relates to a water-based nano anti-counterfeiting ink-jet ink which is prepared from raw materials such as fluorescent composite particles, water-based resin and the like, wherein in the preparation process, in step S1, cerium chloride hexahydrate, oleic acid and 1-octadecene are mixed to prepare a precursor solution, sodium hydroxide, ammonium fluoride and methanol are uniformly mixed to prepare a mixed solution A, the mixed solution A is dropwise added into the precursor solution to prepare a primary material, the primary material is a core-shell structure nano particle prepared based on rare earth elements, the core-shell structure can effectively isolate the quenching effect of surface defects such as nano material dangling bonds and surface organic vibrating groups on fluorescent materials, the luminous efficiency is improved, in step S2, chitosan is used as a carbon source, glacial acetic acid is used as a condensing agent, ethylenediamine is used as a nitrogen doping agent, a fluorescent quantum is prepared by a microwave heating method, and then the fluorescent composite particles are uniformly mixed, and have high luminous efficiency, so that the prepared ink has a fluorescent anti-counterfeiting effect;

the invention also provides a water-based resin, in the preparation process, in the step S1, the bisphenol A and the 1, 6-hexamethylene diisocyanate are mixed in epoxy chloropropane, the bisphenol A and the 1, 6-hexamethylene diisocyanate react to generate an intermediate, then the intermediate reacts with the epoxy chloropropane under the action of sodium hydroxide to generate a water-based epoxy resin primary material, in the step S2, the citric acid is used as a raw material to prepare a nano particle, and the nano particle is blended, extruded and granulated to prepare the water-based resin, so that the water-based resin can be endowed with certain fluorescence performance, and the anti-counterfeiting effect is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

Example 1

The water-based nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 1 part of fluorescent composite particles, 35 parts of aqueous resin, 0.1 part of sodium dodecyl benzene sulfonate, 0.01 part of ethylene glycol monomethyl ether, 1 part of absolute ethyl alcohol and 50 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150r/min, cooling to room temperature after stirring, sequentially adding sodium dodecyl benzene sulfonate and ethylene glycol monomethyl ether, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

The fluorescent composite particle is prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding a mixed solution A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60 ℃ in the dropwise adding process, preserving heat for 30min at the temperature, heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed solution A to the precursor solution to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then placing the slurry in a dialysis bag of 500Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is 2: 3: 0.2.

The mixed solution A is formed by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.5g to 2.0g to 5 mL.

The aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a 35 ℃ water bath, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 30min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin primary material, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution to a reaction kettle, reacting at the temperature of 120 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a 3500 molecular weight dialysis bag for dialysis for 48 hours, collecting dialysate, evaporating by using a rotary evaporator, drying at the temperature of 90 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30mL, adding the nanoparticles into a primary resin material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the primary resin material.

Example 2

The water-based nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 3 parts of fluorescent composite particles, 40 parts of aqueous resin, 0.3 part of sodium dodecyl benzene sulfonate, 0.02 part of ethylene glycol monomethyl ether, 5 parts of absolute ethyl alcohol and 60 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150r/min, cooling to room temperature after stirring, sequentially adding sodium dodecyl benzene sulfonate and ethylene glycol monomethyl ether, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

The fluorescent composite particle is prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding a mixed solution A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60 ℃ in the dropwise adding process, preserving heat for 30min at the temperature, heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed solution A to the precursor solution to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then placing the slurry in a dialysis bag of 500Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is 2: 3: 0.2.

The mixed solution A is formed by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.5g to 2.0g to 5 mL.

The aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a 35 ℃ water bath, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 30min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin primary material, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution to a reaction kettle, reacting at the temperature of 120 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a 3500 molecular weight dialysis bag for dialysis for 48 hours, collecting dialysate, evaporating by using a rotary evaporator, drying at the temperature of 90 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30mL, adding the nanoparticles into a primary resin material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the primary resin material.

Example 3

The water-based nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 8 parts of fluorescent composite particles, 45 parts of aqueous resin, 0.4 part of sodium dodecyl benzene sulfonate, 0.02 part of ethylene glycol monomethyl ether, 8 parts of absolute ethyl alcohol and 75 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150r/min, cooling to room temperature after stirring, sequentially adding sodium dodecyl benzene sulfonate and ethylene glycol monomethyl ether, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

The fluorescent composite particle is prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding a mixed solution A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60 ℃ in the dropwise adding process, preserving heat for 30min at the temperature, heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed solution A to the precursor solution to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then placing the slurry in a dialysis bag of 500Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is 2: 3: 0.2.

The mixed solution A is formed by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.5g to 2.0g to 5 mL.

The aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a 35 ℃ water bath, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 30min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin primary material, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution to a reaction kettle, reacting at the temperature of 120 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a 3500 molecular weight dialysis bag for dialysis for 48 hours, collecting dialysate, evaporating by using a rotary evaporator, drying at the temperature of 90 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30mL, adding the nanoparticles into a primary resin material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the primary resin material.

Example 4

The water-based nano anti-counterfeiting ink-jet ink comprises the following raw materials in parts by weight: 10 parts of fluorescent composite particles, 50 parts of aqueous resin, 0.5 part of sodium dodecyl benzene sulfonate, 0.03 part of ethylene glycol monomethyl ether, 10 parts of absolute ethyl alcohol and 80 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150r/min, cooling to room temperature after stirring, sequentially adding sodium dodecyl benzene sulfonate and ethylene glycol monomethyl ether, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

The fluorescent composite particle is prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding a mixed solution A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60 ℃ in the dropwise adding process, preserving heat for 30min at the temperature, heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed solution A to the precursor solution to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then placing the slurry in a dialysis bag of 500Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is 2: 3: 0.2.

The mixed solution A is formed by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.5g to 2.0g to 5 mL.

The aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a 35 ℃ water bath, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotating speed of 100r/min, controlling the dropwise adding time to be 30min, uniformly stirring and reacting for 2h, then heating to 60 ℃, slowly dropwise adding a sodium hydroxide solution with the mass fraction of 20%, controlling the dropwise adding time to be 15min, reacting for 2h at the temperature, washing for 3 times with deionized water, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare a resin primary material, wherein the weight ratio of bisphenol A to epichlorohydrin is controlled to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate is 3: 1, and the weight ratio of bisphenol A to 20% of the sodium hydroxide solution is 3: 1.5;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution to a reaction kettle, reacting at the temperature of 120 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a 3500 molecular weight dialysis bag for dialysis for 48 hours, collecting dialysate, evaporating by using a rotary evaporator, drying at the temperature of 90 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30mL, adding the nanoparticles into a primary resin material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the primary resin material.

Comparative example 1

This comparative example compares to example 1 with an epoxy resin instead of the water-borne resin.

Comparative example 2

The comparative example is anti-counterfeiting ink-jet ink in the market.

The inks prepared in examples 1 to 4 and comparative examples 1 to 2 were examined for their luminous intensity and stability, and the results are shown in the following table:

stability: the freezing test at 0 ℃ and the heating test at 60 ℃ were carried out for 30 hours for examples 1 to 4 and comparative examples 1 to 2, respectively, and the presence of gelation or coarseness of the ink was observed.

As can be seen from the above table, the luminescence intensities of 551-²) Comparative examples 1 to 2 had emission intensities of 0 to 385 (cd/m)²) (ii) a Examples 1 to 4 did not show a phenomenon in the stability test, comparative example 1 did not show a phenomenon in the stability test, and comparative example 2 showed a gelling phenomenon; therefore, the primary material is core-shell structured nano particles prepared based on rare earth elements, the quenching effect of surface defects such as a nano material dangling bond and a surface organic vibrating group on a fluorescent material can be effectively isolated through the core-shell structure, and the luminous efficiency is improved

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (6)

1. The water-based nano anti-counterfeiting ink-jet ink is characterized by comprising the following raw materials in parts by weight: 1-10 parts of composite particles, 35-50 parts of aqueous resin, 0.1-0.5 part of surfactant, 0.01-0.03 part of drier, 1-10 parts of absolute ethyl alcohol and 50-80 parts of water;

the water-based nano anti-counterfeiting ink-jet ink is prepared by the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65-75 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150-250r/min, cooling to room temperature after stirring, sequentially adding a surfactant and a drier, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.

2. The aqueous nano anti-counterfeiting inkjet ink according to claim 1, wherein the surfactant is any one of sodium dodecyl benzene sulfonate and tween-20, and the drier is any one of isopropanol and ethylene glycol monomethyl ether.

3. The aqueous nano anti-counterfeiting inkjet ink according to claim 1, wherein the fluorescent composite particles are prepared by the following method:

step S1, adding cerium chloride hexahydrate, oleic acid and 1-octadecene into a three-neck flask, magnetically stirring at the rotating speed of 50-100r/min, introducing argon for 30min, heating to 150 ℃, preserving heat at the temperature, magnetically stirring for 10min, standing and cooling to obtain a precursor solution, dropwise adding mixed liquor A into the precursor solution, controlling the dropwise adding time to be 2h, heating to 60-70 ℃ in the dropwise adding process, preserving heat at the temperature for 30min, then heating to 80 ℃, preserving heat for 30min to obtain a primary material, cleaning the primary material with acetone and absolute ethyl alcohol for three times respectively for later use, controlling the dosage ratio of the cerium chloride hexahydrate, the oleic acid and the 1-octadecene to be 0.5 g: 5 mL: 10mL, and controlling the volume ratio of the mixed liquor A to the solution precursor to be 1: 3;

step S2, sequentially adding glacial acetic acid and ethylenediamine with the mass fraction of 10% into a three-neck flask filled with chitosan, magnetically stirring for 30min at the rotating speed of 150 plus 200r/min to prepare slurry, reacting the slurry in a microwave oven for 10min, taking out, standing, cooling, adding deionized water, uniformly stirring for 10min, centrifuging for 3min at the rotating speed of 5000r/min, then putting the slurry into a dialysis bag of 500 plus 800Da for dialysis for 2h to prepare solution B, adding the primary material prepared in the step S1 into the solution B, uniformly mixing, and performing suction filtration to prepare the fluorescent composite particles, wherein the dosage ratio of the chitosan, the 10% glacial acetic acid and the ethylenediamine is controlled to be 1 g: 10mL, and the weight ratio of the slurry, the deionized water and the primary material is controlled to be 2: 3: 0.2-0.5.

4. The aqueous nano anti-counterfeiting ink-jet ink as claimed in claim 3, wherein the mixed solution A is prepared by mixing sodium hydroxide, ammonium fluoride and methanol according to the dosage ratio of 1.0-1.5 g: 2.0 g: 5 mL.

5. The aqueous nano anti-counterfeiting inkjet ink according to claim 1, wherein the aqueous resin is prepared by the following method:

step S11, adding bisphenol A into a three-neck flask, adding epichlorohydrin, introducing nitrogen, heating in a water bath at 35-50 ℃, stirring at a constant speed of 120r/min at 100-, reacting for 2 hours at the temperature, washing for 3 times by using deionized water, standing for layering, collecting an organic phase, distilling under reduced pressure until no fraction appears, preparing a resin primary material, controlling the weight ratio of bisphenol A to epichlorohydrin to be 1: 5, the weight ratio of bisphenol A to 1, 6-hexamethylene diisocyanate to be 3: 1, and the weight ratio of bisphenol A to 20% sodium hydroxide solution to be 3: 1.5-2;

step S12, adding citric acid into a beaker filled with deionized water, stirring at a constant speed to prepare a citric acid aqueous solution, adding ethylenediamine into the citric acid aqueous solution, stirring uniformly, transferring the solution into a reaction kettle, reacting at the temperature of 120-150 ℃ for 5 hours, standing and cooling for 4 hours after the reaction is finished to prepare a solution a, putting the solution a into a dialysis bag with the molecular weight of 3500 for dialysis for 48 hours, collecting the dialysis external solution, evaporating by using a rotary evaporator, drying at the temperature of 90-100 ℃ for 10 hours to prepare nanoparticles, controlling the dosage ratio of the citric acid, the deionized water and the ethylenediamine to be 1 g: 10 mL: 0.30-0.33mL, adding the nanoparticles into a resin primary material, extruding and granulating to prepare the aqueous resin, and controlling the dosage of the nanoparticles to be 10% of the resin primary material.

6. The preparation method of the aqueous nano anti-counterfeiting ink-jet ink according to claim 1, which is characterized by comprising the following steps:

adding the fluorescent composite particles and the water-based resin into deionized water, heating in a water bath at 65-75 ℃, adding absolute ethyl alcohol, magnetically stirring for 30min at the rotating speed of 150-250r/min, cooling to room temperature after stirring, sequentially adding a surfactant and a drier, dropwise adding a sodium hydroxide aqueous solution with the mass fraction of 10% after uniform mixing to adjust the pH until the pH is 9, and sequentially filtering by using micro-nano membranes with the pore diameter of 0.8 mu m and 0.45 mu m to prepare the water-based nano anti-counterfeiting ink-jet ink.