CN112835277A - Preparation method of thermosensitive anti-counterfeiting ink powder - Google Patents
Preparation method of thermosensitive anti-counterfeiting ink powder Download PDFInfo
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Abstract
The invention discloses a preparation method of a thermosensitive anti-counterfeiting ink powder, which comprises the following specific implementation methods: preparing a thermochromic compound; mixing the thermosensitive color-changing compound with the wall material monomer oil phase to form a mixed oil phase; adding the mixed oil phase into a water phase solution in which a surfactant is dissolved, and carrying out shearing emulsification and heating to obtain a thermochromic nanocapsule dispersion liquid; shearing and mixing the thermochromic nanocapsule dispersion liquid, the demolding agent dispersion liquid and the nucleating resin emulsion at a high speed, adjusting the pH value to acidity, adding the coagulant, and heating to obtain a nuclear particle emulsion; adding an ionic shell resin emulsion and a coagulant into the nuclear particle emulsion to coagulate the toner coagulated particles with the nuclear shell structure; and adjusting the pH value of the aggregated particles of the ink powder to be neutral, and heating to obtain the heat-sensitive anti-counterfeiting ink powder. The patterns printed by the anti-counterfeiting ink powder prepared by the method can present different colors at different temperatures, and the anti-counterfeiting ink powder has the advantages of adjustable color-changing temperature, high color-changing speed, various colors, large color contrast before and after color changing and obvious anti-counterfeiting effect.
Description
Technical Field
The invention belongs to the technical field of anti-counterfeiting ink powder, and particularly relates to a preparation method of thermosensitive anti-counterfeiting ink powder.
Background
Increasingly more and more about counterfeit commodities, diversity of commodity types and aesthetic property of printed products put higher requirements on printing anti-counterfeiting materials and technologies. With the development of office automation, the application of laser printing in work and life is increasingly wide, and various tickets, trademarks, outsourcing and the like also replace the traditional printing method by laser printing. The laser printing paper has high paper output speed, simple operation in the ink powder preparation and use processes and less pollution emission, and has wider prospect in anti-counterfeiting application. However, high-quality security toner for laser printers is not uncommon.
Thermochromic materials can be divided into two major classes, namely irreversible thermochromic materials and reversible thermochromic materials according to the reversibility of thermochromic; the organic reversible thermochromic material is more in quantity, and the comprehensive performance of the organic reversible thermochromic material in various thermochromic materials is optimal. The advantages are that: wide temperature sensing color change range (20-200 deg.C), obvious color change, bright color, high color change sensitivity, and low production cost. But the organic reversible thermochromic material still has some performance defects, such as poor thermal stability and working temperature below 200 ℃; the chemical stability is poor, and the discoloration is easily removed under the strong acid or strong alkali condition, which limits the application of the composite material to a certain extent.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a thermosensitive anti-counterfeiting toner, patterns printed by the anti-counterfeiting toner prepared by the method can present different colors at different temperatures, the color-changing temperature is adjustable, the color-changing speed is high, the colors are various, the color contrast before and after color changing is large, and the anti-counterfeiting effect is obvious.
The technical scheme adopted by the invention is as follows:
a preparation method of a thermosensitive anti-counterfeiting ink powder is implemented according to the following steps:
step 1, preparing a thermosensitive color-changing compound;
step 2, mixing the thermosensitive color-changing compound with the wall material monomer oil phase to form a mixed oil phase;
step 3, adding the mixed oil phase into a water phase solution in which a surfactant is dissolved, and carrying out shearing emulsification and heating to obtain a thermochromic nanocapsule dispersion liquid;
step 4, shearing and mixing the thermochromic nanocapsule dispersion liquid, the demolding agent dispersion liquid and the nucleating resin emulsion at a high speed, adjusting the pH value to acidity, adding a coagulant, and heating to obtain a nuclear particle emulsion;
step 5, adding the ionic shell resin emulsion and a coagulant into the nuclear particle emulsion to coagulate the toner coagulated particles with the nuclear shell structure;
and 6, adjusting the pH value of the toner agglutinated particles to be neutral, and heating to obtain the heat-sensitive anti-counterfeiting toner.
Preferably, the specific method for preparing the thermochromic compound in step 1 is as follows:
the coloring agent, the color developing agent and the melting agent are mixed according to the ratio of 1: (1-100): (20-500), heating to a temperature above the melting point of the melting agent, stirring, and reacting to form a homogeneous phase to obtain a thermochromic compound;
wherein the colorant is leuco dye, including fluorane, triarylmethane, phenothiazine, spiropyran, rhodamine B lactam, phthalic acid lactone, indoline, and auramine;
the color developing agent is organic acid or phenolic hydroxyl compound and derivatives thereof;
the melting agent is a low boiling point alcohol.
Preferably, in the step 2, the thermochromic compound and the wall material monomer oil phase are mixed to form a mixed oil phase, specifically:
uniformly mixing the thermosensitive color-changing compound and the wall material monomer oil phase in a molten state according to the mass ratio of 1: 4-4: 1 to form a mixed oil phase;
the wall material monomer oil phase comprises a wall material monomer, a cross-linking agent and an initiator; the cross-linking agent accounts for 0.1-10% of the weight of the wall material monomer, and the initiator accounts for 1-20% of the weight of the wall material monomer.
Preferably, in the step 3, the mixed oil phase is added into an aqueous phase solution in which a surfactant is dissolved, and shearing emulsification and temperature rise are performed to obtain a thermochromic nanocapsule dispersion liquid, specifically:
adding the mixed oil phase into an aqueous phase solution dissolved with a surfactant, carrying out shearing emulsification for 5-30min at the speed of 5000-25000rpm, carrying out ultrasonic homogenization to uniformly disperse the mixed oil phase into the aqueous phase solution in the form of nano-scale droplets to form a miniemulsion, transferring the miniemulsion to a three-neck flask, continuously stirring at the speed of 300-600rpm, heating to 60-95 ℃, and carrying out polymerization reaction for 2-20h to completely convert the monomer into polymer resin to obtain a thermochromic nanocapsule dispersion liquid with the particle size of 100-500 nm;
wherein the mass ratio of the mixed oil phase to the aqueous phase solution is 1: 10-1: 2, and the temperature of the aqueous phase solution is 5-10 ℃ higher than the melting point temperature of the thermochromic composite.
Preferably, the mass ratio of the thermochromic nanocapsule dispersion liquid, the release agent dispersion liquid and the nucleating resin emulsion in step 4 is as follows: (5: 5: 90) - (15: 20: 65).
Wherein, adding a coagulant, and heating to obtain a nuclear particle emulsion, which specifically comprises the following steps: adding agglutinant to agglutinate the nanoparticles into micron-sized particles, and heating to a temperature above the glass transition temperature of the core resin particles and below the glass transition temperature of the shell resin particles to spheroidize the agglutinated particles to form core particle emulsion.
Preferably, the concentration of the release agent dispersion is 10 to 40%, and the particle size is 50 to 300 nm; the concentration of the nucleating resin emulsion is 10-40%, and the particle size is 100-500 nm.
Preferably, the pH is adjusted to 2-5 in step 4.
Preferably, the concentration of the ionic shell resin emulsion in the step 5 is 10-40%, and the particle size is 100-500 nm.
Preferably, the coagulant in step 5 is an inorganic salt, and the dosage of the inorganic salt accounts for 0.01-0.5% of the mass of the nuclear particle emulsion.
Preferably, the temperature in step 6 is raised to above the glass transition temperature of the shell resin particles.
Compared with the prior art, the patterns printed by the anti-counterfeiting ink powder prepared by the invention can present different colors at different temperatures, and the anti-counterfeiting ink powder has the advantages of adjustable color-changing temperature, high color-changing speed, various colors, large color contrast before and after color changing and obvious anti-counterfeiting effect.
Drawings
FIG. 1 is a flow chart of a method for preparing a heat-sensitive anti-counterfeiting toner according to an embodiment of the invention;
FIG. 2 is a microscopic view of an anti-counterfeiting toner prepared by a method for preparing a heat-sensitive anti-counterfeiting toner provided in embodiment 1 of the present invention;
FIG. 3 is an effect diagram of an anti-counterfeiting toner prepared by the method for preparing a thermosensitive anti-counterfeiting toner provided by embodiment 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a thermosensitive anti-counterfeiting toner, which is implemented according to the following steps as shown in figure 1:
step 1, preparing a thermosensitive color-changing compound; the method specifically comprises the following steps:
the coloring agent, the color developing agent and the melting agent are mixed according to the ratio of 1: (1-100): (20-500), heating to a temperature above the melting point of the melting agent, stirring, and reacting to form a homogeneous phase to obtain a thermochromic compound;
wherein, the temperature is required to be heated to 10-50 ℃ above the melting point temperature of the melting agent; the mass ratio of the coloring agent, the color developer and the melting agent is preferably 1: (1-10): (20-200);
the colorant is leuco dye, including fluorane, triarylmethane, phenothiazine, spiropyran, rhodamine B lactam, phthalic acid lactone, indoline, auramine, etc., and can be selected from 2-phenylamino-3-methyl-6-diethylaminofluorane, 2-phenylamino-3-methyl-6-dibutylaminofluorane, 6- (ethyl isoamylamino) -1, 2-benzofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, o-cresol sulfonyl phthalide, dibromo-o-cresol sulfonyl, 10-diethylamino spiro [ isobenzofuran-1 (3H),7- [7H ] benzo [ c ] xanthene ] -3-one, 3-bis (4-dimethylaminophenyl) -6-dimethylamino phthalide, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- (2-methyl-1-octyl-1H-indol-3-yl) furo [3,4-b ] pyridin-5 (7H) -one, 4' - [ (9-butyl-9H-carbazole-3-) methylene ] bis [ N-methyl-N-phenyl ] aniline, 6- (diethylamino) -2- (phenylamino) -spiro [ isobenzofuran-1 (3H),9- [9H ] xanthene ] -3-one, 3-bis (4- (dimethylamino) phenyl) phthalide, spiro (isobenzofuran-1 (3H),9(9H) xanthene-2-carboxylic acid-6- (diethylamino) -3-oxo-ethyl ester or a compound system containing more than one of the xanthene-2-carboxylic acid-6- (diethylamino) -3-oxo-ethyl ester;
the color developing agent is organic acid or phenolic hydroxyl compound and derivatives thereof, and can be one or more compound systems selected from boric acid, bisphenol A, stearic acid, laurate, 8-hydroxyquinoline, benzyl p-hydroxybenzoate, 4-hydroxycoumarin, alpha-naphthol, beta-naphthol, lauric acid, myristic acid, palmitic acid, pyrogallic acid, tannic acid, 2, 6-di-tert-butyl-p-cresol and 4-methoxyphenol;
the melting agent is low boiling point alcohol, and can be one or more than one compound system of octanol, decanol, dodecanol, tetradecanol, hexadecanol and octadecanol;
step 2, mixing the thermosensitive color-changing compound with the wall material monomer oil phase to form a mixed oil phase; the method specifically comprises the following steps:
uniformly mixing the thermosensitive color-changing compound and the wall material monomer oil phase in a molten state according to a mass ratio of 1: 4-4: 1 (preferably 1: 2-2: 1) to form a mixed oil phase;
the wall material monomer oil phase comprises a wall material monomer, a cross-linking agent and an initiator; the cross-linking agent accounts for 0.1-10%, preferably 0.5-5% of the weight of the wall material monomer, and the initiator accounts for 1-20%, preferably 5-15% of the weight of the wall material monomer;
the wall material monomer is a monomer capable of forming a transparent polymer with the glass transition temperature of more than 100 ℃, and is selected from one or more than one of styrene, methyl methacrylate, tert-butyl methacrylate, N-hydroxymethyl acrylamide, maleic acid, acrylonitrile, acrylamide, acrylic acid, methacrylic acid and tetrafluoroethylene;
the cross-linking agent is an oil-soluble compound containing a plurality of unsaturated double bonds, and is selected from one or more than one of divinylbenzene, divinyl sulfone, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, allyl methacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate;
the initiator is oil-soluble azo initiator or peroxide initiator, and is selected from one or more of azobisisoheptonitrile, azobisisobutyronitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, Benzoyl Peroxide (BPO), dilauroyl peroxide (LPO), tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate or tert-butyl peroxyisobutyrate;
step 3, adding the mixed oil phase into a water phase solution in which a surfactant is dissolved, and carrying out shearing emulsification and heating to obtain a thermochromic nanocapsule dispersion liquid, wherein the thermochromic nanocapsule dispersion liquid specifically comprises the following steps:
adding the mixed oil phase into an aqueous phase solution dissolved with a surfactant, carrying out shearing emulsification for 5-30min at the speed of 5000-25000rpm (preferably 10000-20000rpm), carrying out ultrasonic homogenization to uniformly disperse the mixed oil phase in the aqueous phase solution in the form of nano-scale droplets to form a fine emulsion, then transferring the fine emulsion to a three-neck flask, continuously stirring at the speed of 300-600rpm, carrying out polymerization reaction for 2-20h (preferably 5-15h) after heating to 60-95 ℃, completely converting the monomer into polymer resin, and obtaining the thermochromic nanocapsule dispersion with the particle size of 100-500nm (preferably 200-400 nm);
wherein the mass ratio of the mixed oil phase to the aqueous phase solution is 1: 10-1: 2 (preferably 1: 5-1: 3), and the temperature of the aqueous phase solution is 5-10 ℃ higher than the melting point temperature of the thermochromic composite;
the concentration of the surfactant in water is 0.1-6%, preferably 0.5-3%;
step 4, shearing and mixing the thermochromic nanocapsule dispersion liquid, the demolding agent dispersion liquid and the nucleating resin emulsion at a high speed, adjusting the pH value to acidity, adding an agglutinant to agglutinate the nanoparticles into micron-sized particles, and then heating to a temperature higher than the glass transition temperature of the nucleating resin particles and lower than the glass transition temperature of the shell resin particles to spheroidize the agglutinated particles to form the nuclear particle emulsion;
the preparation of the release agent dispersion liquid is that the release agent is melted at the temperature higher than the melting point of the release agent, the surfactant is added, and the deionized water is added in batches by utilizing the phase transition principle to obtain the release agent dispersion liquid with certain solid content; the release agent is selected from one or more than one of low molecular weight polyolefin wax and grease synthetic wax: polyolefin waxes include polyethylene wax (PE wax) and polypropylene wax (PP wax); the oil and fat synthetic wax comprises pentaerythritol tetrastearate, pentaerythritol tetra behenate, dipentaerythritol hexapalmitate, dipentaerythritol hexamyristate or dipentaerythritol hexalaurate, etc.;
the nucleating resin emulsion is prepared by a seed emulsion polymerization method, and the monomer is mainly selected from a monovinyl monomer and comprises one or more than one of the following materials: aromatic vinyl monomers such as styrene, methylstyrene or α -methylstyrene; one or more kinds of monomers such as acrylic acids (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl methacrylate, glycidyl (meth) acrylate, and lauryl (meth) acrylate);
preferably, the concentration of the release agent dispersion is 10-40%, preferably 20-30%, and the particle size is 50-300nm, preferably 100-200 nm. The concentration of the nucleating resin emulsion is 10-40%, preferably 20-30%, and the particle size is 100-500nm, preferably 200-400 nm. The pH of the system during the agglutination is 2-5, preferably 3-4. The glass transition temperature of the nucleating resin is preferably 40-60 ℃, and the particle size of the core particles is 0.5-3 μm, preferably 1-2 μm;
step 5, adding the ionic shell resin emulsion and a coagulant into the nuclear particle emulsion to coagulate the toner coagulated particles with the nuclear shell structure;
step 6, adjusting the pH value of the toner agglutinated particles to be neutral, heating to a temperature higher than the glass transition temperature of the shell resin particles, and fusing the core and the shell to obtain the heat-sensitive anti-counterfeiting toner;
the ionic shell resin emulsion is prepared by copolymerizing a high glass transition temperature monomer and an ionic monomer by a seed emulsion polymerization method;
the high Tg monomer is mainly selected from one or more than one of monomers capable of forming polymers with the glass transition temperature of over 60 ℃ such as styrene, methyl methacrylate, tert-butyl methacrylate, N-hydroxymethyl acrylamide, acrylonitrile, acrylamide, hydroxypropyl methacrylate and the like;
the ionic monomer includes a cationic monomer and an anionic monomer. The cationic monomer mainly comprises tertiary amine and quaternary ammonium salt monomers containing unsaturated double bonds, such as one or more of oleyl dimethyl tertiary amine, oleic acid amide propyl dimethyl tertiary amine (PKO-O), erucic acid amide propyl dimethyl tertiary amine (PKO-E) and oleyl dimethyl benzyl ammonium chloride;
the anionic monomer mainly comprises sulfonic acid, sulfuric acid, phosphoric acid, carboxylic acid and acrylic acid monomers containing unsaturated double bonds, such as one or more materials of (methyl) acrylic acid, vinylsulfonic acid (sodium and potassium), sodium styrenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS), allylsulfonic acid (sodium and potassium), methacrylic sulfonic acid (sodium and potassium) and 3-sulfopropyl acrylic acid (sodium and potassium);
the concentration of the ionic shell resin emulsion is 10-40%, preferably 20-30%, the particle size is 100-500nm, preferably 200-400nm, and the glass transition temperature is preferably 70-90 ℃; the pH of the system during the agglutination is 2-5, preferably 3-4. The size of the core-shell structure toner particles is 5-20 μm, preferably 7-11 μm;
in the prepared toner particles, the colorant accounts for 2% -15%, preferably 5% -10%, the release agent accounts for 2% -25%, preferably 5% -15%, and the sum of the nucleating resin and the ionic shell resin accounts for 60% -90%. The ionic shell resin accounts for 5% -40%, preferably 10% -30% of the total resin in the toner particles. The dosage of the ionic monomer is 1-20%, preferably 3-15% of the total amount of the shell resin monomer. (ii) a
The agglutinant used in the preparation process is selected from inorganic salt capable of performing agglutination, such as one or more of sodium chloride, potassium chloride, magnesium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, and zinc sulfate. The amount of the coagulant to be used is generally 0.01 to 0.5%, preferably 0.1 to 0.4% by mass of the mixed emulsion to be coagulated.
The surfactant used in the preparation process is selected from one or more than one compound system of cationic surfactant, anionic surfactant and nonionic surfactant. Wherein the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, dodecyl trimethyl chloride, dodecyl sniffed pyridine, dodecyl dimethyl benzyl ammonium chloride, alkyl dimethyl hydroxyethyl quaternary ammonium salt and alkyl dimethyl hydroxyethyl quaternary ammonium salt; the anionic surfactant is at least one of fatty alcohol-polyoxyethylene ether carboxylate, sodium stearate, linear alkyl benzene sodium sulfonate, branched alkyl benzene sodium sulfonate, diisopropyl sodium zeityl sulfonate, dibutyl sodium zeityl sulfonate, alkyl sodium sulfonate, alpha-olefin sodium sulfonate, alpha-sulfo fatty acid, linear alkyl sulfate, branched alkyl sodium sulfate, fatty alcohol-polyoxyethylene ether sulfate and styrene-maleic anhydride copolymer; the nonionic surfactant is at least one of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octadecyl ether, sorbitol monooleate polyoxyethylene ether, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkanolamide and polyoxyethylene alkanolamide.
In the thermosensitive anti-counterfeiting ink powder particles provided by the embodiment, the colorant is a thermochromic nanocapsule, so that the thermosensitive anti-counterfeiting ink powder particles have a good anti-counterfeiting effect; the capsule wall of the thermochromic microcapsule is polymer resin, so that the environmental stability of the colorant is improved, the compatibility of the colorant and the core resin is improved, the uniform dispersion of the colorant in toner particles is facilitated, and the problems of poor charging stability and the like caused by colorant leakage and leakage thereof are avoided; the toner particles are of a core-shell structure, and have the nucleating resin with low glass transition temperature and the ionic shell resin with high glass transition temperature, so that the toner particles have uniform and stable charging property and good low-temperature fixing property and environmental stability; in the process for preparing the ink powder, the ink powder particles are formed by agglutinating thermochromic nanocapsule dispersion liquid, demolding agent dispersion liquid and nucleating resin emulsion, so that the efficient function separation effect is achieved, and the prepared ink powder particles are good in sphericity, narrow in particle distribution, good in electrification and good in durability.
Example 1
The embodiment 1 of the invention provides a preparation method of a thermosensitive anti-counterfeiting ink powder, which comprises the following specific implementation methods:
firstly, 1 part of 2-phenylamino-3-methyl-6-dibutylamino fluorane, 2 parts of bisphenol A and 60 parts of n-tetradecanol are placed in a three-necked bottle provided with a stirring device, the temperature is increased to 90 ℃, and the temperature is kept unchanged under the condition of stirring speed of 600rpm for reaction for 1 hour to obtain a thermochromic compound in a molten state;
cooling a three-necked flask containing 60 parts of thermochromic compound to 50 ℃, adding 60 parts of methyl methacrylate, 0.6 part of divinylbenzene and 2 parts of azobisisobutyronitrile, keeping the temperature at 50 ℃, stirring until the mixture is uniformly mixed, pouring the mixture into 400 parts of aqueous phase solution dissolved with 2 parts of sodium dodecyl sulfate and 2 parts of polyvinylpyrrolidone (PVP-K30), keeping the temperature of the aqueous phase solution at 50 ℃, dispersing under a high-speed dispersion machine at a stirring speed of 20000rpm for 10min, then homogenizing for 10min by ultrasonic to obtain miniemulsion with oil phase and water phase mixed uniformly, at this time, the particle size of oil drop is about 300nm, transferring the miniemulsion into a three-neck bottle with oil bath temperature of 50 ℃, heating to 80 ℃ under the condition of stirring speed of 600rpm, reacting for 5h to obtain thermochromic nanocapsule dispersion liquid, wherein the particle size of the thermochromic nanocapsule is about 300nm, and the thermochromic nanocapsule dispersion liquid is heated to above 40 ℃ to generate a black-to-colorless fading phenomenon;
60 parts of ester wax (WE-4, manufactured by Nippon fat Co., Ltd.), 3.6 parts of stabilizer fatty alcohol-polyoxyethylene ether (Hokka), 0.6 part of dispersant 2774 (from Claien) and 1.8 parts of emulsifier hexadecyl trimethyl ammonium bromide are added into a three-neck flask, the temperature is raised to 95 ℃ by water bath heating, 200 parts of deionized water is added in batches under the condition that the stirring speed is 300rpm, and a stable wax dispersion liquid is prepared by a phase transition method, wherein the particle size of wax particles is about 100 nm;
then 2.5 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 76 parts of styrene and 24 parts of n-butyl acrylate are added, the mixture is dispersed under a high-speed dispersion machine with the stirring speed of 5000rpm for 5min to obtain monomer emulsion, 120 parts of water and 0.5 part of sodium dodecyl sulfate are added into a three-neck flask and stirred until the mixture is dissolved, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, 25 parts of monomer emulsion are added, 1ml of 25% ammonium persulfate aqueous solution is dripped after the temperature is raised to 80 ℃ under the condition of the stirring speed of 300rpm, after reaction is carried out for 1h, the rest monomer emulsion is dripped into the three-neck flask at the speed of 2ml/min, during the period, 8ml of 25% ammonium persulfate aqueous solution is added in 4 times, after the dripping is finished, the reaction is continued for 3h, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, obtaining a nucleated resin emulsion, wherein the Tg of the nucleated resin particles is 45.1 ℃, and the particle size is about 300 nm;
placing 10 parts of thermochromic nanocapsule dispersion liquid, 15 parts of demolding agent dispersion liquid and 100 parts of nucleating resin emulsion into a three-neck flask, adding 125 parts of deionized water, dispersing for 30min at a stirring speed of 1500rpm, reducing the stirring speed to 1000rpm, keeping the pH of the system to 3-4 by dropwise adding 10% sulfuric acid aqueous solution, slowly dropwise adding 30ml of 2% aluminum chloride aqueous solution, heating to 50 ℃ after dropwise adding, and continuously stirring for 1h to obtain a large amount of aggregated particles with the particle size of 1-2 microns;
finally, 3 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 82 parts of styrene, 12 parts of n-butyl acrylate and 6 parts of sodium styrene sulfonate are added, and the mixture is dispersed in a high-speed dispersion machine at the stirring speed of 5000rpm for 5min to obtain the monomer emulsion. Adding 120 parts of water and 0.6 part of sodium dodecyl sulfate into a three-neck flask, stirring until the water and the sodium dodecyl sulfate are dissolved, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, adding 25 parts of monomer emulsion, heating to 80 ℃ under the condition of stirring speed of 300rpm, dropwise adding 1ml of 25% ammonium persulfate aqueous solution, reacting for 1h, dropwise adding the rest monomer emulsion into the three-neck flask at the speed of 2ml/min, adding 8ml of 25% ammonium persulfate aqueous solution for 4 times during the reaction, continuing to react for 3h after the dropwise addition is finished, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, and obtaining nucleating resin emulsion, wherein the Tg of the nucleating resin particles is 70.9 ℃, and the particle size is about 300 nm;
and dropwise adding 10% sodium hydroxide aqueous solution to adjust the pH value of the core particle emulsion to 7-8, slowly dropwise adding 30 parts of ionic shell resin emulsion, dispersing at the stirring speed of 1500rpm for 30min, reducing the stirring speed to 1000rpm, dropwise adding 10% sulfuric acid aqueous solution to keep the pH value of the system to 3-4, slowly dropwise adding 15ml of 2% aluminum chloride aqueous solution, and continuously stirring for 1h after dropwise adding is finished, so that a large number of core-shell structure agglutinated particles appear in the system, and the particle size is 2-3 mu m. Heating to 70 ℃, the core-shell structure agglutinated particles begin to agglomerate, continuously stirring until the core-shell structure agglutinated particles grow to 5-10 mu m, adjusting the system pH to 7-8 by dripping 10% of sodium hydroxide aqueous solution, heating to 90 ℃, carrying out spheroidization treatment on the ink powder particles, and keeping for 2h to obtain the thermosensitive anti-counterfeiting ink powder particles with good particle sphericity and narrow particle size distribution, as shown in figure 2;
the image printed by the toner particles is heated to above 41 ℃ to generate a color change from black to colorless, and has a good anti-counterfeiting function, as shown in figure 3.
Example 2
The embodiment 2 of the invention provides a preparation method of a thermosensitive anti-counterfeiting ink powder, which comprises the following specific implementation methods:
firstly, 0.6 part of dibromo-o-cresol sulfolene, 9 parts of stearic acid and 60 parts of n-dodecanol are put into a three-necked bottle provided with a stirring device, the temperature is raised to 90 ℃, and the temperature is kept unchanged under the condition of stirring speed of 600rpm for reaction for 1 hour to obtain a thermal discoloration compound in a molten state;
cooling a three-necked flask containing 60 parts of thermochromic compound to 50 ℃, adding 60 parts of methyl methacrylate, 0.6 part of divinylbenzene and 2 parts of azobisisobutyronitrile, keeping the temperature at 50 ℃, stirring until the mixture is uniformly mixed, pouring the mixture into 400 parts of aqueous phase solution dissolved with 2 parts of sodium dodecyl sulfate and 2 parts of polyvinylpyrrolidone (PVP-K30), keeping the temperature of the aqueous phase solution at 50 ℃, dispersing under a high-speed dispersion machine at a stirring speed of 20000rpm for 10min, then homogenizing for 10min by ultrasonic to obtain miniemulsion with oil phase and water phase mixed uniformly, at this time, the particle size of oil drop is about 300nm, transferring the miniemulsion into a three-neck bottle with oil bath temperature of 50 ℃, heating to 80 ℃ under the condition of stirring speed of 600rpm, reacting for 5h to obtain thermochromic nanocapsule dispersion liquid, wherein the particle size of the thermochromic nanocapsule is about 300nm, and the thermochromic nanocapsule dispersion liquid is heated to above 40 ℃ to generate a black-to-colorless fading phenomenon;
60 parts of ester wax (WE-4, manufactured by Nippon fat Co., Ltd.), 3.6 parts of stabilizer fatty alcohol-polyoxyethylene ether (Hokka), 0.6 part of dispersant 2774 (from Claien) and 1.8 parts of emulsifier hexadecyl trimethyl ammonium bromide are added into a three-neck flask, the temperature is raised to 95 ℃ by water bath heating, 200 parts of deionized water is added in batches under the condition that the stirring speed is 300rpm, and a stable wax dispersion liquid is prepared by a phase transition method, wherein the particle size of wax particles is about 100 nm;
then 2.5 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 76 parts of styrene and 24 parts of n-butyl acrylate are added, the mixture is dispersed under a high-speed dispersion machine with the stirring speed of 5000rpm for 5min to obtain monomer emulsion, 120 parts of water and 0.5 part of sodium dodecyl sulfate are added into a three-neck flask and stirred until the mixture is dissolved, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, 25 parts of monomer emulsion are added, 1ml of 25% ammonium persulfate aqueous solution is dripped after the temperature is raised to 80 ℃ under the condition of the stirring speed of 300rpm, after reaction is carried out for 1h, the rest monomer emulsion is dripped into the three-neck flask at the speed of 2ml/min, during the period, 8ml of 25% ammonium persulfate aqueous solution is added in 4 times, after the dripping is finished, the reaction is continued for 3h, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, obtaining a nucleated resin emulsion, wherein the Tg of the nucleated resin particles is 45.1 ℃, and the particle size is about 300 nm;
placing 10 parts of thermochromic nanocapsule dispersion liquid, 15 parts of demolding agent dispersion liquid and 100 parts of nucleating resin emulsion into a three-neck flask, adding 125 parts of deionized water, dispersing for 30min at a stirring speed of 1500rpm, reducing the stirring speed to 1000rpm, keeping the pH of the system to 3-4 by dropwise adding 10% sulfuric acid aqueous solution, slowly dropwise adding 30ml of 2% aluminum chloride aqueous solution, heating to 50 ℃ after dropwise adding, and continuously stirring for 1h to obtain a large amount of aggregated particles with the particle size of 1-2 microns;
finally, 3 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 82 parts of styrene, 12 parts of n-butyl acrylate and 6 parts of sodium styrene sulfonate are added, and the mixture is dispersed in a high-speed dispersion machine at the stirring speed of 5000rpm for 5min to obtain the monomer emulsion. Adding 120 parts of water and 0.6 part of sodium dodecyl sulfate into a three-neck flask, stirring until the mixture is dissolved, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, adding 25 parts of monomer emulsion, heating to 80 ℃ under the condition of stirring speed of 300rpm, dropwise adding 1ml of 25% ammonium persulfate aqueous solution, reacting for 1h, dropwise adding the rest monomer emulsion into the three-neck flask at the speed of 2ml/min, adding 8ml of 25% ammonium persulfate aqueous solution for 4 times during the reaction, continuing to react for 3h after the dropwise addition is finished, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, and obtaining a shell-forming resin emulsion, wherein the Tg of the shell-forming resin particles is 70.9 ℃, and the particle size is about 300 nm;
and dropwise adding 10% sodium hydroxide aqueous solution to adjust the pH value of the core particle emulsion to 7-8, slowly dropwise adding 30 parts of ionic shell resin emulsion, dispersing at the stirring speed of 1500rpm for 30min, reducing the stirring speed to 1000rpm, dropwise adding 10% sulfuric acid aqueous solution to keep the pH value of the system to 3-4, slowly dropwise adding 15ml of 2% aluminum chloride aqueous solution, and continuously stirring for 1h after dropwise adding is finished, so that a large number of core-shell structure agglutinated particles appear in the system, and the particle size is 2-3 mu m. And heating to 70 ℃, the core-shell structure agglutinated particles begin to agglomerate, continuously stirring until the core-shell structure agglutinated particles grow to 5-10 mu m, adjusting the pH of the system to 7-8 by dripping 10% of sodium hydroxide aqueous solution, heating to 90 ℃, carrying out spheroidization treatment on the ink powder particles, and keeping for 2 hours to obtain the thermosensitive anti-counterfeiting ink powder particles with good particle sphericity and narrow particle size distribution.
The image printed by the toner particles is heated to more than 25 ℃ to generate color change from orange red to light yellow, and the anti-counterfeiting function is good.
Example 3
The embodiment 3 of the invention provides a preparation method of a thermosensitive anti-counterfeiting ink powder, which comprises the following specific implementation methods:
firstly, placing 1.2 parts of 3, 3-bis (4- (dimethylamino) phenyl) phthalide, 2.4 parts of 4-hydroxycoumarin and 60 parts of n-hexadecanol in a three-necked bottle with a stirring device, heating to 90 ℃, and keeping the temperature unchanged under the condition of stirring speed of 600rpm for reaction for 1h to obtain a thermochromic compound in a molten state;
cooling a three-necked flask containing 60 parts of thermochromic compound to 50 ℃, adding 60 parts of methyl methacrylate, 0.6 part of divinylbenzene and 2 parts of azobisisobutyronitrile, keeping the temperature at 50 ℃, stirring until the mixture is uniformly mixed, pouring the mixture into 400 parts of aqueous phase solution dissolved with 2 parts of sodium dodecyl sulfate and 2 parts of polyvinylpyrrolidone (PVP-K30), keeping the temperature of the aqueous phase solution at 50 ℃, dispersing under a high-speed dispersion machine at a stirring speed of 20000rpm for 10min, then homogenizing for 10min by ultrasonic to obtain miniemulsion with oil phase and water phase mixed uniformly, at this time, the particle size of oil drop is about 300nm, transferring the miniemulsion into a three-neck bottle with oil bath temperature of 50 ℃, heating to 80 ℃ under the condition of stirring speed of 600rpm, reacting for 5h to obtain thermochromic nanocapsule dispersion liquid, wherein the particle size of the thermochromic nanocapsule is about 300nm, and the thermochromic nanocapsule dispersion liquid is heated to above 40 ℃ to generate a black-to-colorless fading phenomenon;
60 parts of ester wax (WE-4, manufactured by Nippon fat Co., Ltd.), 3.6 parts of stabilizer fatty alcohol-polyoxyethylene ether (Hokka), 0.6 part of dispersant 2774 (from Claien) and 1.8 parts of emulsifier hexadecyl trimethyl ammonium bromide are added into a three-neck flask, the temperature is raised to 95 ℃ by water bath heating, 200 parts of deionized water is added in batches under the condition that the stirring speed is 300rpm, and a stable wax dispersion liquid is prepared by a phase transition method, wherein the particle size of wax particles is about 100 nm;
then 2.5 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 76 parts of styrene and 24 parts of n-butyl acrylate are added, the mixture is dispersed under a high-speed dispersion machine with the stirring speed of 5000rpm for 5min to obtain monomer emulsion, 120 parts of water and 0.5 part of sodium dodecyl sulfate are added into a three-neck flask and stirred until the mixture is dissolved, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, 25 parts of monomer emulsion are added, 1ml of 25% ammonium persulfate aqueous solution is dripped after the temperature is raised to 80 ℃ under the condition of the stirring speed of 300rpm, after reaction is carried out for 1h, the rest monomer emulsion is dripped into the three-neck flask at the speed of 2ml/min, during the period, 8ml of 25% ammonium persulfate aqueous solution is added in 4 times, after the dripping is finished, the reaction is continued for 3h, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, obtaining a nucleated resin emulsion, wherein the Tg of the nucleated resin particles is 45.1 ℃, and the particle size is about 300 nm;
placing 10 parts of thermochromic nanocapsule dispersion liquid, 15 parts of demolding agent dispersion liquid and 100 parts of nucleating resin emulsion into a three-neck flask, adding 125 parts of deionized water, dispersing for 30min at a stirring speed of 1500rpm, reducing the stirring speed to 1000rpm, keeping the pH of the system to 3-4 by dropwise adding 10% sulfuric acid aqueous solution, slowly dropwise adding 30ml of 2% aluminum chloride aqueous solution, heating to 50 ℃ after dropwise adding, and continuously stirring for 1h to obtain a large amount of aggregated particles with the particle size of 1-2 microns;
finally, 3 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 82 parts of styrene, 12 parts of n-butyl acrylate and 6 parts of sodium styrene sulfonate are added, and the mixture is dispersed in a high-speed dispersion machine at the stirring speed of 5000rpm for 5min to obtain the monomer emulsion. Adding 120 parts of water and 0.6 part of sodium dodecyl sulfate into a three-neck flask, stirring until the mixture is dissolved, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, adding 25 parts of monomer emulsion, heating to 80 ℃ under the condition of stirring speed of 300rpm, dropwise adding 1ml of 25% ammonium persulfate aqueous solution, reacting for 1h, dropwise adding the rest monomer emulsion into the three-neck flask at the speed of 2ml/min, adding 8ml of 25% ammonium persulfate aqueous solution for 4 times during the reaction, continuing to react for 3h after the dropwise addition is finished, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, and obtaining a shell-forming resin emulsion, wherein the Tg of the shell-forming resin particles is 70.9 ℃, and the particle size is about 300 nm;
and dropwise adding 10% sodium hydroxide aqueous solution to adjust the pH value of the core particle emulsion to 7-8, slowly dropwise adding 30 parts of ionic shell resin emulsion, dispersing at the stirring speed of 1500rpm for 30min, reducing the stirring speed to 1000rpm, dropwise adding 10% sulfuric acid aqueous solution to keep the pH value of the system to 3-4, slowly dropwise adding 15ml of 2% aluminum chloride aqueous solution, and continuously stirring for 1h after dropwise adding is finished, so that a large number of core-shell structure agglutinated particles appear in the system, and the particle size is 2-3 mu m. And heating to 70 ℃, the core-shell structure agglutinated particles begin to agglomerate, continuously stirring until the core-shell structure agglutinated particles grow to 5-10 mu m, adjusting the pH of the system to 7-8 by dripping 10% of sodium hydroxide aqueous solution, heating to 90 ℃, carrying out spheroidization treatment on the ink powder particles, and keeping for 2 hours to obtain the thermosensitive anti-counterfeiting ink powder particles with good particle sphericity and narrow particle size distribution.
The image printed by the toner particles is heated to above 52 ℃ to generate the color change from blue green to light green, and the anti-counterfeiting function is good.
Example 4
The embodiment 4 of the invention provides a preparation method of a thermosensitive anti-counterfeiting ink powder, which comprises the following specific implementation methods:
firstly, 1 part of 3, 3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, 4 parts of bisphenol A, 43 parts of n-tetradecanol and 22 parts of n-hexadecanol are placed in a three-neck flask provided with a stirring device, the temperature is increased to 90 ℃, and the temperature is kept unchanged under the condition of stirring speed of 600rpm for reaction for 1 hour to obtain a thermochromic compound in a molten state;
cooling a three-necked flask containing 60 parts of thermochromic compound to 50 ℃, adding 60 parts of methyl methacrylate, 0.6 part of divinylbenzene and 2 parts of azobisisobutyronitrile, keeping the temperature at 50 ℃, stirring until the mixture is uniformly mixed, pouring the mixture into 400 parts of aqueous phase solution dissolved with 2 parts of sodium dodecyl sulfate and 2 parts of polyvinylpyrrolidone (PVP-K30), keeping the temperature of the aqueous phase solution at 50 ℃, dispersing under a high-speed dispersion machine at a stirring speed of 20000rpm for 10min, then homogenizing for 10min by ultrasonic to obtain miniemulsion with oil phase and water phase mixed uniformly, at this time, the particle size of oil drop is about 300nm, transferring the miniemulsion into a three-neck bottle with oil bath temperature of 50 ℃, heating to 80 ℃ under the condition of stirring speed of 600rpm, reacting for 5h to obtain thermochromic nanocapsule dispersion liquid, wherein the particle size of the thermochromic nanocapsule is about 300nm, and the thermochromic nanocapsule dispersion liquid is heated to above 40 ℃ to generate a black-to-colorless fading phenomenon;
60 parts of ester wax (WE-4, manufactured by Nippon fat Co., Ltd.), 3.6 parts of stabilizer fatty alcohol-polyoxyethylene ether (Hokka), 0.6 part of dispersant 2774 (from Claien) and 1.8 parts of emulsifier hexadecyl trimethyl ammonium bromide are added into a three-neck flask, the temperature is raised to 95 ℃ by water bath heating, 200 parts of deionized water is added in batches under the condition that the stirring speed is 300rpm, and a stable wax dispersion liquid is prepared by a phase transition method, wherein the particle size of wax particles is about 100 nm;
then 2.5 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 76 parts of styrene and 24 parts of n-butyl acrylate are added, the mixture is dispersed under a high-speed dispersion machine with the stirring speed of 5000rpm for 5min to obtain monomer emulsion, 120 parts of water and 0.5 part of sodium dodecyl sulfate are added into a three-neck flask and stirred until the mixture is dissolved, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, 25 parts of monomer emulsion are added, 1ml of 25% ammonium persulfate aqueous solution is dripped after the temperature is raised to 80 ℃ under the condition of the stirring speed of 300rpm, after reaction is carried out for 1h, the rest monomer emulsion is dripped into the three-neck flask at the speed of 2ml/min, during the period, 8ml of 25% ammonium persulfate aqueous solution is added in 4 times, after the dripping is finished, the reaction is continued for 3h, the pH value is adjusted to be 7-8 by dripping 10% of sodium hydroxide aqueous solution, obtaining a nucleated resin emulsion, wherein the Tg of the nucleated resin particles is 45.1 ℃, and the particle size is about 300 nm;
placing 10 parts of thermochromic nanocapsule dispersion liquid, 15 parts of demolding agent dispersion liquid and 100 parts of nucleating resin emulsion into a three-neck flask, adding 125 parts of deionized water, dispersing for 30min at a stirring speed of 1500rpm, reducing the stirring speed to 1000rpm, keeping the pH of the system to 3-4 by dropwise adding 10% sulfuric acid aqueous solution, slowly dropwise adding 30ml of 2% aluminum chloride aqueous solution, heating to 50 ℃ after dropwise adding, and continuously stirring for 1h to obtain a large amount of aggregated particles with the particle size of 1-2 microns;
finally, 3 parts of sodium dodecyl sulfate is dissolved in 120 parts of water, 82 parts of styrene, 12 parts of n-butyl acrylate and 6 parts of sodium styrene sulfonate are added, and the mixture is dispersed in a high-speed dispersion machine at the stirring speed of 5000rpm for 5min to obtain the monomer emulsion. Adding 120 parts of water and 0.6 part of sodium dodecyl sulfate into a three-neck flask, stirring until the mixture is dissolved, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, adding 25 parts of monomer emulsion, heating to 80 ℃ under the condition of stirring speed of 300rpm, dropwise adding 1ml of 25% ammonium persulfate aqueous solution, reacting for 1h, dropwise adding the rest monomer emulsion into the three-neck flask at the speed of 2ml/min, adding 8ml of 25% ammonium persulfate aqueous solution for 4 times during the reaction, continuing to react for 3h after the dropwise addition is finished, adjusting the pH to 7-8 by dropwise adding 10% of sodium hydroxide aqueous solution, and obtaining a shell-forming resin emulsion, wherein the Tg of the shell-forming resin particles is 70.9 ℃, and the particle size is about 300 nm;
and dropwise adding 10% sodium hydroxide aqueous solution to adjust the pH value of the core particle emulsion to 7-8, slowly dropwise adding 30 parts of ionic shell resin emulsion, dispersing at the stirring speed of 1500rpm for 30min, reducing the stirring speed to 1000rpm, dropwise adding 10% sulfuric acid aqueous solution to keep the pH value of the system to 3-4, slowly dropwise adding 15ml of 2% aluminum chloride aqueous solution, and continuously stirring for 1h after dropwise adding is finished, so that a large number of core-shell structure agglutinated particles appear in the system, and the particle size is 2-3 mu m. And heating to 70 ℃, the core-shell structure agglutinated particles begin to agglomerate, continuously stirring until the core-shell structure agglutinated particles grow to 5-10 mu m, adjusting the pH of the system to 7-8 by dripping 10% of sodium hydroxide aqueous solution, heating to 90 ℃, carrying out spheroidization treatment on the ink powder particles, and keeping for 2 hours to obtain the thermosensitive anti-counterfeiting ink powder particles with good particle sphericity and narrow particle size distribution.
The image printed by the toner particles is heated to above 33 ℃ to generate the color change from violet to light blue, and the anti-counterfeiting function is good.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the thermosensitive anti-counterfeiting ink powder is characterized by comprising the following steps:
step 1, preparing a thermosensitive color-changing compound;
step 2, mixing the thermosensitive color-changing compound with the wall material monomer oil phase to form a mixed oil phase;
step 3, adding the mixed oil phase into a water phase solution in which a surfactant is dissolved, and carrying out shearing emulsification and heating to obtain a thermochromic nanocapsule dispersion liquid;
step 4, shearing and mixing the thermochromic nanocapsule dispersion liquid, the demolding agent dispersion liquid and the nucleating resin emulsion at a high speed, adjusting the pH value to acidity, adding a coagulant, and heating to obtain a nuclear particle emulsion;
step 5, adding the ionic shell resin emulsion and a coagulant into the nuclear particle emulsion to coagulate the toner coagulated particles with the nuclear shell structure;
and 6, adjusting the pH value of the toner agglutinated particles to be neutral, and heating to obtain the heat-sensitive anti-counterfeiting toner.
2. The preparation method of the thermosensitive anti-counterfeiting toner according to claim 1, wherein the specific method for preparing the thermosensitive color-changing compound in the step 1 is as follows:
the coloring agent, the color developing agent and the melting agent are mixed according to the ratio of 1: (1-100): (20-500), heating to a temperature above the melting point of the melting agent, stirring, and reacting to form a homogeneous phase to obtain a thermochromic compound;
wherein the colorant is leuco dye, including fluorane, triarylmethane, phenothiazine, spiropyran, rhodamine B lactam, phthalic acid lactone, indoline, and auramine;
the color developing agent is organic acid or phenolic hydroxyl compound and derivatives thereof;
the melting agent is a low boiling point alcohol.
3. The preparation method of the thermosensitive anti-counterfeiting toner according to claim 2, wherein the thermosensitive color-changing compound and the wall material monomer oil phase are mixed in the step 2 to form a mixed oil phase, specifically:
uniformly mixing the thermosensitive color-changing compound and the wall material monomer oil phase in a molten state according to the mass ratio of 1: 4-4: 1 to form a mixed oil phase;
the wall material monomer oil phase comprises a wall material monomer, a cross-linking agent and an initiator; the cross-linking agent accounts for 0.1-10% of the weight of the wall material monomer, and the initiator accounts for 1-20% of the weight of the wall material monomer.
4. The preparation method of the heat-sensitive anti-counterfeiting toner according to claim 3, wherein the mixed oil phase is added into the water phase solution dissolved with the surfactant in the step 3, and the shearing emulsification and the temperature rise are carried out to obtain the thermochromic nanocapsule dispersion liquid, which specifically comprises the following steps:
adding the mixed oil phase into an aqueous phase solution dissolved with a surfactant, carrying out shearing emulsification for 5-30min at the speed of 5000-25000rpm, carrying out ultrasonic homogenization to uniformly disperse the mixed oil phase into the aqueous phase solution in the form of nano-scale droplets to form a miniemulsion, transferring the miniemulsion to a three-neck flask, continuously stirring at the speed of 300-600rpm, heating to 60-95 ℃, and carrying out polymerization reaction for 2-20h to completely convert the monomer into polymer resin to obtain a thermochromic nanocapsule dispersion liquid with the particle size of 100-500 nm;
wherein the mass ratio of the mixed oil phase to the aqueous phase solution is 1: 10-1: 2, and the temperature of the aqueous phase solution is 5-10 ℃ higher than the melting point temperature of the thermochromic composite.
5. The preparation method of the thermosensitive anti-counterfeiting toner according to claim 4, wherein the mass ratio of the thermochromic nanocapsule dispersion liquid, the release agent dispersion liquid and the nucleating resin emulsion in the step 4 is as follows: (5: 5: 90) - (15: 20: 65)
Wherein, adding a coagulant, and heating to obtain a nuclear particle emulsion, which specifically comprises the following steps: adding agglutinant to agglutinate the nanoparticles into micron-sized particles, and heating to a temperature above the glass transition temperature of the core resin particles and below the glass transition temperature of the shell resin particles to spheroidize the agglutinated particles to form core particle emulsion.
6. The method for preparing a heat-sensitive anti-counterfeiting toner according to claim 5, wherein the concentration of the releasing agent dispersion is 10-40%, and the particle size is 50-300 nm; the concentration of the nucleating resin emulsion is 10-40%, and the particle size is 100-500 nm.
7. The method for preparing a heat-sensitive anti-counterfeiting toner according to claim 6, wherein the pH is adjusted to 2-5 in the step 4.
8. The method for preparing a heat-sensitive anti-counterfeiting toner according to any one of claims 1 to 7, wherein the concentration of the ionic shell resin emulsion in the step 5 is 10 to 40%, and the particle size is 100-500 nm.
9. The method for preparing a heat-sensitive anti-counterfeiting toner according to claim 8, wherein the coagulant in the step 5 is an inorganic salt, and the amount of the inorganic salt is 0.01 to 0.5 percent of the mass of the core particle emulsion.
10. The method for producing a thermosensitive anti-counterfeit toner according to claim 9, wherein the temperature in step 6 is raised above the glass transition temperature of the shell resin particles.
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| CN113998920A (en) * | 2021-11-30 | 2022-02-01 | 山东康洁利新材料有限公司 | Production method of artificial quartz stone color-changing plate |
| CN114958092A (en) * | 2022-06-01 | 2022-08-30 | 东莞职业技术学院 | Temperature-change anti-counterfeiting ink and preparation method and application thereof |
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| CN102713762A (en) * | 2009-11-13 | 2012-10-03 | 百乐墨水株式会社 | Thermochromic color-memorization type toner, cartridge including same housed therein, image formation apparatus, cartridge set, and image formation apparatus set |
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| CN101046651A (en) * | 2006-03-28 | 2007-10-03 | 富士施乐株式会社 | Image forming apparatus, image forming method and toner |
| CN102713762A (en) * | 2009-11-13 | 2012-10-03 | 百乐墨水株式会社 | Thermochromic color-memorization type toner, cartridge including same housed therein, image formation apparatus, cartridge set, and image formation apparatus set |
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