CN113004884A

CN113004884A - Invisible anti-counterfeiting material composition, preparation process and application thereof

Info

Publication number: CN113004884A
Application number: CN202110225111.2A
Authority: CN
Inventors: 祁泽林; 莫浩昌; 刘永军
Original assignee: Guangdong Mina Anti Counterfeiting Technology Co ltd
Current assignee: Guangdong Mina Anti Counterfeiting Technology Co ltd
Priority date: 2021-03-01
Filing date: 2021-03-01
Publication date: 2021-06-22
Anticipated expiration: 2041-03-01
Also published as: CN113004884B

Abstract

The invention relates to the technical field of anti-counterfeiting materials, in particular to an invisible anti-counterfeiting material composition, a preparation process and application thereof, wherein the invisible anti-counterfeiting material composition comprises the following raw materials: nano photochromic material, dispersant, filler, surfactant high polymer, reinforcing agent and solvent; each part of the nano photochromic material comprises 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane Y₂O₂S:Eu³⁺And benzoic acid-o-phenanthroline-europium ternary complex. The invisible anti-counterfeiting material composition can be stably adhered to the surface of a substrate, is not easy to fall off, is suitable for various substrates, is combined with a packaging film, a packaging box, an anti-counterfeiting label and a loading container, has an invisible effect under a visible light state, has different visual or imaging effects under the irradiation of light of different wave bands, and has a good anti-counterfeiting effect.

Description

Invisible anti-counterfeiting material composition, preparation process and application thereof

Technical Field

The invention relates to the technical field of anti-counterfeiting materials, in particular to a invisible anti-counterfeiting material composition, a preparation process and application thereof.

Background

The brand effect is an effect brought by brands to enterprises and is a continuation of value in the commercial society, but for the anti-counterfeiting maintenance of genuine products of brand products in China at present, anti-counterfeiting labels are basically arranged on packaging boxes or packaging bags for packaging the brand products, such as expensive consumer products such as skin care products, drinks and the like, and are arranged on the packaging boxes or the packaging bags, so that consumers can verify the genuine products or inquire anti-counterfeiting information in time when purchasing the products.

However, there are some packages or bags on which counterfeit products are loaded and which are originally provided with anti-counterfeit labels in the market, so that consumers can falsely or falsely take apart the packages or bags, and find that the purchased products are counterfeit products, and the containers on which the products are loaded do not have related anti-counterfeit marks, or the stickup anti-counterfeit marks are easy to counterfeit, which results in that the consumer has a high difficulty in maintaining the rights of the counterfeit products.

For the anti-counterfeiting mark arranged on the container for loading the product, the anti-counterfeiting ink is printed on the anti-counterfeiting label in the market at present, then the anti-counterfeiting label is pasted on the surface of the container for loading, but the anti-counterfeiting label is easy to drop or pasted on the surface of the container for counterfeiting the product, the anti-counterfeiting performance of the container for loading the product is still low, the anti-counterfeiting ink is printed or coated on the surface of the container for loading at present, the anti-counterfeiting ink is easy to drop, and the like, so that the anti-counterfeiting performance is reduced.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the invisible anti-counterfeiting material composition which can be stably adhered to the surface of a container for loading products, is suitable for glass loading containers and plastic loading containers, can be suitable for packaging films, packaging boxes and anti-counterfeiting labels, is stably adhered to a base body, is not easy to fall off, has a colorless transparent effect in a normal state, has a fluorescent effect under ultraviolet irradiation, and has a good anti-counterfeiting effect.

The invention also aims to provide a preparation process of the invisible anti-counterfeiting material composition, which is convenient to operate and easy to control, the prepared invisible anti-counterfeiting material composition has stable performance, can be applied to the surface of a loading container or applied to a packaging film, a packaging box and an anti-counterfeiting label after being mixed with a curing agent, and forms an anti-counterfeiting mark after being cured, thereby having a fluorescent anti-counterfeiting effect.

The invention also aims to provide the application of the invisible anti-counterfeiting material composition, which can be applied to packaging films, packaging boxes and anti-counterfeiting labels, and has wide application range and high practicability.

The invention further aims to provide an application of the invisible anti-counterfeiting material composition in a loading container, which is applicable to the loading container made of plastic or glass materials.

The purpose of the invention is realized by the following technical scheme: the invisible anti-counterfeiting material composition comprises the following raw materials in parts by weight:

each part by weight of the nano photochromic material comprises 1.5 to 2.5 parts by weight of 3-diethylamino-6-methyl-7-phenylaminofluorane, 1 to 2 parts by weight of 2'- (dibenzylamino) -6' - (diethylamino) fluorane and 0.5 to 0.8 part by weight of Y₂O₂S:Eu³⁺And 2-3 parts by weight of benzoic acid-phenanthroline-europium ternary complex.

This application is through adopting above-mentioned material preparation stealthy anti-counterfeiting material composition, and the material dispersibility is good, and nanometer photochromic material is difficult for subsiding, the layering, and stability is high to stable with plastics material, glass material, paper, adhesion, be difficult for droing, be colorless transparent under the normal state, present fluorescence state under the effect of ultraviolet ray, have anti-counterfeiting effect.

The adopted nano photochromic material is prepared by matching substances including organic components, complexes and the like according to a specific dosage, has a stable invisible anti-counterfeiting effect, is uniformly dispersed in the composition, is colorless and transparent in a normal state and is in an invisible state, and can be in a fluorescent state under ultraviolet rays, so that the nano photochromic material is convenient to identify; preferably, the adopted 3-diethylamino-6-methyl-7-phenylamino fluorane is selected from Wuhan Haishan science and technology limited company, is light yellow powder, can be stably dispersed in a composition system, and the adopted 2'- (dibenzylamino) -6' - (diethylamino) fluorane is selected from Hubei Wankusan chemical industry limited company, has high stability, contains unsaturated bonds in the 3-diethylamino-6-methyl-7-phenylamino fluorane and the 2'- (dibenzylamino) -6' - (diethylamino) fluorane, can convert ultraviolet light with shorter wavelength into visible light with longer wavelength, and can present fluorescence effect; and Y used₂O₂S:Eu³⁺Yttrium oxysulfide nano particles are used as a carrier, Eu³⁺As an activator, the Eu is loaded on a carrier under the action of ultraviolet light³⁺The jump emits red long afterglow, the stability is high, and the jump is mixed with the 3-diethylamino-6-methyl-7-phenylaminofluorane and the 2'- (dibenzylamino) -6' - (diethylamino) fluorane, so that the invisible anti-counterfeiting material has more obvious fluorescence effect under ultraviolet light, the distinguishability is high, and particularly in a glass material, the fluorescence effect generates refraction in a glass medium and enhances the fluorescence effect; the benzoic acid-o-phenanthroline-europium ternary complex is used for coordinating rare earth metal europium with organic matters, and the ligand transfers energy to the rare earth metal after absorbing light energy, so that the Eu in a luminescence center has a fluorescence enhancement effect, the electron donating property of benzoic acid and the range of common rail pi bonds in benzaldehyde can enhance the fluorescence luminescence property of the benzoic acid-o-phenanthroline-europium ternary complex, and the benzoic acid-o-phenanthroline-europium ternary complex is not easy to oxidize and stable in performance, and can improve the fluorescence effect of the anti-counterfeiting material composition when being mixed with other nano photochromic materials. The compounded nano photochromic material has a nano particle size of 150-200nm, can be stably attached to the surface of a substrate, and improves the application stability of the invisible anti-counterfeiting material composition.

The adopted dispersing agent can improve the dispersibility of materials in the invisible anti-counterfeiting material composition, and reduce the agglomeration or sedimentation phenomenon of the nano photochromic material and the filler, so that the anti-counterfeiting material composition has certain glossiness and a smooth surface; the adopted filler can be used as a carrier of the nano photochromic material to improve the dispersibility of the nano photochromic material in a system, and can improve the adhesiveness of the anti-counterfeiting material composition on the surface of a matrix and improve the application stability. The adopted surfactant can reduce the interfacial tension among the high polymer, the nano photochromic material, the filling material and the solvent, improve the compatibility among the powder, the high polymer and the solvent and further improve the dispersion uniformity of the material; the adopted high polymer provides a main body adhered to the substrate for the anti-counterfeiting material composition, improves the adhesion stability of the anti-counterfeiting material composition on the surface of the substrate, and is not easy to fall off. The adopted firming agent can improve the adhesion of the invisible anti-counterfeiting material composition and improve the adhesion fastness of the invisible anti-counterfeiting material composition on the surface of a substrate; the adopted solvent improves the dispersibility of the anti-counterfeiting material composition, so that the anti-counterfeiting material composition has certain flow casting performance and is easy to apply on the surface of a matrix.

Preferably, the nano photochromic material is a modified nano photochromic material subjected to load modification treatment, and the modified nano photochromic material is prepared by the following steps:

step A: adding polyoxyethylene lauryl ether into the mixed solvent, then adding a silane coupling agent, mixing and stirring to prepare a modified base solution;

and B: 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺And mixing the benzoic acid-o-phenanthroline-europium ternary complex, adding the mixture into the modified base solution, stirring and dispersing the mixture uniformly at the temperature of 70-80 ℃, then preserving the heat for 20-25min, adding silicon dioxide, mixing, preserving the heat for 2-3h at the temperature of 70-80 ℃, and drying to obtain the modified nano photochromic material.

Because the nano photochromic material contains organic components, coordination compounds and other substances, the nano photochromic material has low dispersion compatibility with materials such as high polymers, fillers and the like, the nano photochromic material is easy to influence the dispersion effect of the nano photochromic material in a system, and further has the phenomena of agglomeration, deposition and the like, the adhesion of the anti-counterfeiting material composition on a substrate is influenced, and the fluorescent color development effect is influenced. Therefore, in the application, the nano photochromic material is mixed with the silicon dioxide for heat preservation, the nano photochromic material is modified, the nano photochromic material is grafted in the silicon dioxide, the dispersibility of the silicon dioxide in a high polymer and a solvent is utilized to improve the dispersion performance of the nano photochromic material, and the bonding performance of the silicon dioxide and a matrix is utilized to improve the adhesion stability of the anti-counterfeiting material composition on the matrix. In the step A, firstly, lauryl alcohol polyoxyethylene ether is added into a mixed solvent to prepare a surface active solution, then a silane coupling agent is added into the surface active solution, then a nano photochromic material is added, so that the nano photochromic material is uniformly dispersed in a system under the action of the surface active agent, and is mixed with the silane coupling agent in advance and subjected to heat preservation treatment, so that the silane coupling agent is firstly grafted with the nano photochromic material, after silicon dioxide is subsequently added, the silane coupling agent modifies the surface of the silicon dioxide under the heat preservation condition to improve the loading capacity of the surface of the silicon dioxide as a graft, and meanwhile, the nano photochromic material uniformly dispersed with the coupling agent in advance is quickly loaded on the surface of the silicon dioxide, so that the dispersibility of the nano photochromic material in an anti-counterfeiting material polymer is improved by utilizing the silicon dioxide.

Preferably, in the step A, the mixing weight ratio of the lauryl alcohol polyoxyethylene ether to the mixed solvent to the silane coupling agent is 1:15-20:0.5-0.8, the mixing ratio of the lauryl alcohol polyoxyethylene ether to the mixed solvent to the silane coupling agent is controlled, so that the modified base solution can be uniformly dispersed, and then the nano photochromic material and the silicon dioxide are added, so that the grafting is stable, the grafting rate is high, and the dispersibility of the nano photochromic material in the anti-counterfeiting material composition is improved; the mixed solvent is composed of isopropanol and tetraethoxysilane in a weight ratio of 2-3:1, and by adopting the mixture of isopropanol and tetraethoxysilane as the mixed solvent, lauryl alcohol polyoxyethylene ether, a silane coupling agent, a nano photochromic material and silicon dioxide can be uniformly dispersed, so that the load stability of the silicon dioxide on the nano photochromic material is improved, and the dispersibility of the nano photochromic material in the anti-counterfeiting material composition is improved, wherein the adopted tetraethoxysilane can improve the light transmittance of the nano photochromic material and improve the fluorescence effect of the modified nano photochromic material; the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane, and silicon hydroxyl on the surface of silicon dioxide are subjected to dehydration condensation to form a Si-O-Si bond and are grafted on the surface of the silicon dioxide, so that the silicon dioxide generates large steric hindrance acting force and good dispersibility, and the load of the nano photochromic material is improved; in the step B, the mixing weight ratio of the nano photochromic material to the modified base solution to the silicon dioxide is 5:10-12:2-4, and the nano photochromic material and the silicon dioxide can be grafted at two ends of the coupling agent component in the modified base solution respectively under the heat preservation condition by controlling the mixing weight ratio of the nano photochromic material to the modified base solution to the silicon dioxide, so that the loading rate of the nano photochromic material on the surface of the silicon dioxide is improved, and the dispersion uniformity of the nano photochromic material in the anti-counterfeiting material composition is further improved. The particle size of the prepared modified nano photochromic material is 180-230nm by loading the nano photochromic material on silicon dioxide, and the modified nano photochromic material has good dispersibility in an anti-counterfeiting material composition system.

Preferably, the silica is pretreated silica, and the specific steps are as follows:

step (1): calcining and cooling the silicon dioxide; mixing with nitric acid solution, stirring at 70-80 deg.C for 5-6h, filtering, washing with deionized water, vacuum filtering, and drying at 110-120 deg.C to constant weight;

step (2): performing microwave treatment on the silicon dioxide dried in the step (1), adding the silicon dioxide subjected to microwave treatment into a sand core funnel, introducing nitrogen for 5-6h, wherein the nitrogen firstly passes through the bottom of a saturated sodium bromide solution and then passes through the silicon dioxide to obtain microwave silicon dioxide;

and (3): dissolving gamma-aminopropyltriethoxysilane and isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate in xylene, stirring in the atmosphere of nitrogen protection, adding the microwave silicon dioxide obtained in the step (2) while stirring, stirring and reacting for 24-28h at the temperature of 75-83 ℃, filtering, extracting the solid obtained by filtering in a Soxhlet extractor for 20-24h by using toluene, and then drying in vacuum to obtain the pretreated silicon dioxide.

The method has the advantages that the silicon dioxide is pretreated through the steps, the silicon dioxide can be quickly grafted when being added into a system of the nano photochromic material and the coupling agent, the grafting stability of the silicon dioxide and the filler component in the anti-counterfeiting material composition can be improved, and the dispersibility of the nano photochromic material and the filler can be improved. Wherein, the mesh number of the silicon dioxide in the step (1) is 40-60 meshes, the specific surface area is 330-350m²The silica can be activated under the heat preservation treatment of calcination and nitric acid, so that the number of the hydroxyl groups on the surface of the silica is increased under the microwave treatment in the step (2), the grafting rate of the surface of the silica and the nano photochromic material is improved, the silica is treated by adopting nitrogen passing through a saturated sodium bromide solution after the microwave treatment, the airflow speed of the nitrogen is stable, the hydration treatment can be carried out under the fluidized state of the silica treatment, the stability of the hydroxyl groups on the surface of the silica is improved, the silica treated by the microwave is added into a dispersion system of gamma-aminopropyltriethoxysilane and isopropyl dioleate acyloxy (dioctylphosphoryloxy) titanate in the step (3), so that the coupling agent is grafted and stabilized on the surface of the silica, wherein the aminopropyl of the gamma-aminopropyltriethoxysilane can be coupled with a high polymer, ethoxy couplable filler, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate couplable filler, further adopting the pretreated silicon dioxide to improve the dispersibility of the pretreated silicon dioxide with high polymer and filler, and grafting the nanometer photochromic material which is coupled and modified in advance on the surface of the silicon dioxide, then utilizing the pretreated silicon dioxide to improve the dispersibility among the nanometer photochromic material, filler and high polymer, so that the prepared anti-counterfeiting material composition has uniform material dispersion and uniform fluorescence effect under the ultraviolet condition, and simultaneously grafting the isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate on the surface of the silicon dioxide, thereby improving the dispersibility of the silicon dioxide in coating applicationThe adhesion on the substrate can be improved by the application of the security material composition on the substrate by using the silica after the pretreatment.

Preferably, in the step (1), the calcination temperature is 500-520 ℃, the calcination time is 40-60min, and the silica can be activated by controlling the calcination temperature and time of the silica, so that the generation rate of hydroxyl groups on the surface of the silica in the subsequent microwave treatment is improved; the concentration of the nitric acid solution is 1-1.5mol/L, the mixing mass ratio of the silicon dioxide to the nitric acid is 2:5-12, and the silicon dioxide can be acidified by controlling the concentration of the nitric acid solution and the mixing mass ratio of the nitric acid solution to the silicon dioxide, so that the number of hydroxyl groups on the surface of the subsequent silicon dioxide is promoted; the microwave power of the microwave treatment in the step (2) is 700-800W, the microwave time is 2-3min, and a large number of hydroxyl groups can be generated on the surface of the silicon dioxide by controlling the microwave power and the microwave time, so that the subsequent bonding rate of the silicon dioxide and the coupling agent is improved, and the grafting rate is improved; in the step (3), the mixing mass ratio of the gamma-aminopropyltriethoxysilane, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the dimethylbenzene is 3: 40-50, the dispersity of the coupling modifier can be improved by controlling the mixing mass ratio of the gamma-aminopropyltriethoxysilane, the isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the xylene, the grafting rate and the grafting uniformity after the silicon dioxide is added are further promoted, the dispersity between the pretreated silicon dioxide and the nano photochromic material, the filling material and the high polymer is further improved, the coating adhesiveness of the invisible anti-counterfeiting material composition on the surface of the substrate is improved, and the invisible anti-counterfeiting material composition is not easy to fall off; in the step (3), the temperature of vacuum drying is 90-100 ℃, the vacuum drying time is 5-6h, the vacuum degree is-0.05' -0.12MPa, the vacuum degree, the temperature and the time of vacuum drying are controlled, so that the silicon dioxide subjected to grafting pretreatment can be dried quickly, and the condition that polymerization is found among coupled grafts under the environment of heat and oxygen to influence the subsequent grafting stability with the nano photochromic material, the filling material and the high polymer is avoided.

Preferably, the dispersant is at least one of polyvinyl alcohol, dispersant BYK-193 and dispersant BYK-185; the adopted dispersing agent can improve the dispersibility of materials in the invisible anti-counterfeiting material composition, and reduce the agglomeration or sedimentation phenomenon of the nano photochromic material and the filler, so that the anti-counterfeiting material composition has certain glossiness and smooth surface.

Preferably, the filler is a mixture of nano bentonite and calcium carbide in a weight ratio of 3-4: 1.

The filler can improve the dispersibility of the nano photochromic material in a system, on the other hand, the adhesion of the anti-counterfeiting material composition on the surface of a matrix can be improved, the application stability is improved, the filler is stably combined with silicon dioxide under the grafting effect of isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate, the adhesion stability of the anti-counterfeiting material composition on the surface of the matrix can be promoted through the silicon dioxide and the filler, the nano photochromic material is grafted on the surface of the silicon dioxide, and the dispersibility of the nano photochromic material in the composition system can be improved by utilizing the filler and the silicon dioxide. The nano bentonite is selected from Hangzhou Fumei new material company, has good dust prevention and sagging resistance, can improve the tape casting performance of the anti-counterfeiting material composition on the surface of a substrate, has high transparency, is transparent when being dispersed in the anti-counterfeiting material composition, does not influence the fluorescence effect of the nano photochromic material, and can enable the anti-counterfeiting material composition to have yellowing resistance. The adopted calcium carbonate has larger specific surface area, high transparency and good stability, is transparent when being dispersed in the anti-counterfeiting material composition, does not influence the fluorescence effect of the nano photochromic material, can improve the adhesiveness of the anti-counterfeiting material composition on a substrate by utilizing the specific surface area, and is not easy to fall off.

Preferably, the surfactant is at least one of nonylphenol polyether-10, polysorbate-20 and coco diethanolamide.

The surfactant can reduce the interfacial tension among the high polymer, the nano photochromic material, the filler and the solvent, improve the compatibility among the powder, the high polymer and the solvent and further improve the dispersion uniformity of the material; the adopted nonyl phenol polyether-10 and coconut diethanolamide are transparent, do not influence the fluorescence effect of the nano photochromic material, have good wetting, dispersing and solubilizing effects, and can improve the compatibility among materials; the adopted polysorbate-20 has more hydrophilic groups, namely polyoxyethylene groups in molecules, has strong hydrophilicity, can improve the interfacial tension of water in a solvent, and improves the dispersibility of materials in the solvent.

Preferably, the high polymer is one of polyester resin, polyurethane resin, epoxy resin and alkyd resin.

The high polymer has stable performance, can be used as a main component in the invisible anti-counterfeiting material composition, has good adhesion and good dispersibility in a solvent, ensures that the invisible anti-counterfeiting material composition has excellent casting performance, can be uniformly cast on a substrate, and can be cured to form a stable invisible anti-counterfeiting structure with high stability.

Preferably, the fastness enhancing agent is CC-08 type fastness reinforcing agent; can assist in improving the adhesion fastness of the invisible anti-counterfeiting material composition on the surface of the substrate, so that the invisible anti-counterfeiting material composition is not easy to fall off on the surface of the substrate and has high stability.

Preferably, the solvent comprises 2-5 parts by weight of ethylene glycol, 3-4 parts by weight of ethyl acetate and 5 parts by weight of water per part by weight of the solvent. By adopting the composite solvent, the dispersibility of the material can be improved, the invisible anti-counterfeiting material composition has good ductility, the ductility on the surface of the substrate is stable, and the stable invisible anti-counterfeiting structure is prepared after curing and molding.

The other purpose of the invention is realized by the following technical scheme: the preparation process of the invisible anti-counterfeiting material composition comprises the following steps:

the method comprises the following steps: adding a surfactant and a high polymer into a solvent with three-half dosage, and stirring and dispersing for 15-20min under the conditions that the temperature is 35-40 ℃ and the rotating speed is 800-1000rpm to prepare a phase A;

step two: adding the nano photochromic material, the dispersing agent and the filler into the rest solvent, and homogenizing for 8-10min under the condition that the rotating speed is 2000-2500rpm to prepare a phase B;

step three: stirring the phase B under the condition of the rotation speed of 1200-plus 1500rpm, adding the phase A, adding a reinforcing agent after the phase A is added, uniformly dispersing, and then preserving the heat for 2-2.5h at the temperature of 50-60 ℃ to prepare the invisible anti-counterfeiting material composition.

The preparation process is convenient to operate and easy to control, the prepared invisible anti-counterfeiting material composition is stable in performance, can be applied to the surface of a loading container after being mixed with a curing agent, can also be applied to a packaging film, a packaging box and an anti-counterfeiting label, forms an anti-counterfeiting mark after being cured, and has a fluorescent anti-counterfeiting effect. Firstly adding a high polymer and a surfactant into a part of solvent in the first step, stirring and dispersing at the rotating speed of a specific thermometer, dispersing the high polymer in the system in advance, simultaneously adding a nano photochromic material, a dispersing agent and a filler into the rest solvent in the second step, homogenizing uniformly, improving the dispersibility of the powder raw material, adding the pre-dispersed high polymer material into the powder raw material in the third step, improving the dispersibility of the high polymer material and the powder raw material, easily causing the phenomenon of uneven dispersion of the powder raw material if the B phase of the powder raw material is added into the A phase of the high polymer material, and finally adding a reinforcing agent and carrying out heat preservation treatment to ensure that the grafted silicon dioxide is fully connected with the high polymer and improve the dispersibility of the nano photochromic material in the high polymer and the system.

The other purpose of the invention is realized by the following technical scheme: the invisible anti-counterfeiting material composition can be applied to packaging films, packaging boxes or anti-counterfeiting labels.

The invisible anti-counterfeiting material composition prepared by the method can be applied to packaging films, packaging boxes and anti-counterfeiting labels, can be applied in modes of transfer printing, rolling, spraying, printing (such as ink jet, gravure, flexography, offset printing and silk screen printing) and the like, and has wide application range and high practicability.

The other purpose of the invention is realized by the following technical scheme: the application of the invisible anti-counterfeiting material composition in the loading container comprises the following steps:

the method comprises the following steps: laser engraving image-text information on the surface of the loading container to form an engraved groove;

step two: adding photoinitiator which accounts for 0.5-2% of the amount of the invisible anti-counterfeiting material composition into the invisible anti-counterfeiting material composition, uniformly stirring, applying the mixture into the engraved groove, and curing to form a three-dimensional image-text in the engraved groove.

The application of the invisible anti-counterfeiting material composition in the loading container is applicable to the loading container made of plastic or glass materials, the surface of the loading container is made into the carved groove by utilizing a laser carving means, carved image-text information is formed, the invisible anti-counterfeiting material composition is mixed with a light curing agent and then applied to the carved groove, the inner groove wall of the carved groove forms a micro concave-convex structure due to the laser carving means, the adhesion stability of the invisible anti-counterfeiting material composition in the carved groove can be improved, the anti-counterfeiting image-text information which is in a three-dimensional effect under ultraviolet irradiation after photocuring forming is compared with plane anti-counterfeiting ink on the market, the invisible anti-counterfeiting material composition has a better anti-counterfeiting effect, the loading container with the three-dimensional anti-counterfeiting effect is high in imitation cost, and the anti-counterfeiting effect is achieved for luxury goods loading containers. Especially for expensive products such as skin care products, wines and the like at present, the anti-counterfeiting mark can be identified through the invisible fluorescent anti-counterfeiting image-text information on the surface of the container loaded with the skin care products and the water wine, so that the anti-counterfeiting mark effect is improved.

Wherein the laser energy of the laser engraving is 800-; the photoinitiator is formed by mixing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 2-isopropyl thioxanthone in a weight ratio of 1:1-2, and can shorten the curing time of the invisible anti-counterfeiting material composition and improve the curing and forming efficiency, wherein the irradiation wavelength of photocuring is 360-400nm, and the irradiation time is 2-4min, so that the invisible anti-counterfeiting material composition in the carved groove can be stably cured and formed.

The invention has the beneficial effects that: the invisible anti-counterfeiting material composition can be stably adhered to the surface of a substrate, is suitable for glass loading containers and plastic loading containers, can also be suitable for packaging films, packaging boxes and anti-counterfeiting labels, has a colorless transparent effect in a normal state, has a fluorescent effect under ultraviolet irradiation, and has a good anti-counterfeiting effect.

The preparation process of the invisible anti-counterfeiting material composition is convenient to operate and easy to control, the prepared invisible anti-counterfeiting material composition has stable performance, can be applied to a substrate after being mixed with a curing agent, forms an anti-counterfeiting mark after being cured, and has a fluorescent anti-counterfeiting effect.

The invisible anti-counterfeiting material composition can be applied to packaging films, packaging boxes and anti-counterfeiting labels, can be applied to loading containers made of plastics or glass materials, can be used for making carved grooves on the surfaces of the loading containers by laser carving means to form carved graphic and text information, can be mixed with curing agents and then is applied to the carved grooves, and the inner groove walls of the carved grooves form tiny concave-convex structures by the laser carving means, so that the adhesion stability of the invisible anti-counterfeiting material composition in the carved grooves can be improved, the solidified and molded anti-counterfeiting graphic and text information has a three-dimensional effect under the irradiation of ultraviolet light, and the invisible anti-counterfeiting material composition is good in three-dimensional anti-counterfeiting effect, wide in application range and high in practicability.

Detailed Description

The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.

Example 1

The invisible anti-counterfeiting material composition comprises the following raw materials in parts by weight:

each part of the nano photochromic material comprises 1.5 parts of 3-diethylamino-6-methyl-7-phenylaminofluorane, 2 parts of 2'- (dibenzylamino) -6' - (diethylamino) fluorane and 0.5 part of Y₂O₂S:Eu³⁺And 2 parts by weight of benzoic acid-o-phenanthroline-europium ternary complex.

The particle size of the nano photochromic material is 150nm, and the filler is a mixture of nano bentonite and calcium carbide in a weight ratio of 3-4: 1.

The solvent comprises 2-5 parts by weight of ethylene glycol, 4 parts by weight of ethyl acetate and 5 parts by weight of water.

The preparation process of the invisible anti-counterfeiting material composition comprises the following steps:

the method comprises the following steps: adding surfactant and high polymer into three-half amount of solvent, stirring and dispersing at 35 deg.C and 1000rpm for 15min to obtain phase A;

step two: adding the nano photochromic material, the dispersing agent and the filling material into the rest solvent, and homogenizing for 10min under the condition that the rotating speed is 2000rpm to prepare a phase B;

step three: stirring the phase B under the condition of the rotating speed of 1200rpm, adding the phase A, adding the CC-08 type fastness reinforcing agent after the phase A is added, uniformly dispersing, and then preserving heat for 2.5 hours at the temperature of 50 ℃ to prepare the invisible anti-counterfeiting material composition.

The invisible anti-counterfeiting material composition is applied to a glass loading container, and specifically comprises the following steps:

the method comprises the following steps: laser engraving graph and text information on the surface of a 53-degree Maotai wine bottle flying in Guizhou, wherein the laser energy is 800W, the laser temperature is 150 ℃, the laser time is 25s, and engraved grooves are formed, and the average groove depth of the engraved grooves is 0.3 cm;

step two: adding a photoinitiator accounting for 0.5 percent of the using amount of the invisible anti-counterfeiting material composition into the invisible anti-counterfeiting material composition, uniformly stirring, applying the mixture into a carved groove, and irradiating for 4min under the condition that the irradiation wavelength is 360nm to form a three-dimensional image-text in the carved groove.

In the second step, the photoinitiator is formed by mixing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 2-isopropyl thioxanthone according to the weight ratio of 1:1.

Example 2

each part of the nano photochromic material comprises 2 parts of 3-diethylamino-6-methyl-7-phenylaminofluorane, 1.5 parts of 2'- (dibenzylamino) -6' - (diethylamino) fluorane and 0.56 part of Y₂O₂S:Eu³⁺And 2.5 parts by weight of benzoic acid-phenanthroline-europium ternary complex.

The particle size of the nano photochromic material is 180nm, and the filler is a mixture of nano bentonite and calcium carbide in a weight ratio of 3.5: 1.

The solvent comprises 3.5 parts by weight of ethylene glycol, 3.5 parts by weight of ethyl acetate and 5 parts by weight of water per part by weight of the solvent.

the method comprises the following steps: adding surfactant and high polymer into three-half amount of solvent, stirring and dispersing at 38 deg.C and 900rpm for 18min to obtain phase A;

step two: adding the nano photochromic material, the dispersing agent and the filler into the rest solvent, and homogenizing for 9min under the condition that the rotation speed is 2300rpm to prepare a phase B;

step three: stirring the phase B under the condition of the rotating speed of 1300rpm, adding the phase A, adding the CC-08 type fastness reinforcing agent after the phase A is added, uniformly dispersing, and then preserving heat for 2.2 hours at 55 ℃ to prepare the invisible anti-counterfeiting material composition.

the method comprises the following steps: laser engraving graph and text information on the surface of a 53-degree Maotai wine bottle flying in Guizhou, wherein the laser energy is 1000W, the laser temperature is 1670 ℃, and the laser time is 20s, so that engraved grooves are formed, and the average groove depth of the engraved grooves is 0.5 cm;

step two: adding a photoinitiator which accounts for 1% of the using amount of the invisible anti-counterfeiting material composition into the invisible anti-counterfeiting material composition, uniformly stirring, applying the mixture into the engraved groove, and irradiating for 3min under the condition that the irradiation wavelength is 380nm to form a three-dimensional image-text in the engraved groove.

In the second step, the photoinitiator is formed by mixing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 2-isopropyl thioxanthone according to the weight ratio of 1: 1.5.

Example 3

each part of the nano photochromic material comprises 2.5 parts of 3-diethylamino-6-methyl-7-phenylaminofluorane, 1 part of 2'- (dibenzylamino) -6' - (diethylamino) fluorane and 0.8 part of Y₂O₂S:Eu³⁺And 3 parts by weight of benzoic acid-phenanthroline-europium ternary complex.

The particle size of the nano photochromic material is 200nm, and the filler is a mixture of nano bentonite and calcium carbide in a weight ratio of 4: 1.

The solvent comprises 5 parts by weight of ethylene glycol, 3 parts by weight of ethyl acetate and 5 parts by weight of water per part by weight of the solvent.

the method comprises the following steps: adding surfactant and high polymer into three-half amount of solvent, stirring and dispersing at 40 deg.C and 800rpm for 20min to obtain phase A;

step two: adding the nano photochromic material, the dispersing agent and the filling material into the rest solvent, and homogenizing for 8min under the condition that the rotating speed is 2500rpm to prepare a phase B;

step three: stirring the phase B under the condition of the rotating speed of 1500rpm, adding the phase A, adding the CC-08 type fastness reinforcing agent after the phase A is added, uniformly dispersing, and then preserving heat for 2 hours at 60 ℃ to prepare the invisible anti-counterfeiting material composition.

the method comprises the following steps: laser engraving graph and text information on the surface of a 53-degree Maotai wine bottle flying in Guizhou, wherein the laser energy is 1200W, the laser temperature is 170 ℃, and the laser time is 15s, so that engraved grooves are formed, and the average groove depth of the engraved grooves is 0.8 cm;

step two: adding a photoinitiator accounting for 2 percent of the using amount of the invisible anti-counterfeiting material composition into the invisible anti-counterfeiting material composition, uniformly stirring, applying the mixture into the engraved groove, and irradiating for 2min under the condition that the irradiation wavelength is 400nm to form a three-dimensional image-text in the engraved groove.

In the second step, the photoinitiator is formed by mixing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 2-isopropyl thioxanthone according to the weight ratio of 1: 2.

Example 4

This embodiment differs from embodiment 2 described above in that:

the nanometer photochromic material is a modified nanometer photochromic material subjected to load modification treatment, and is prepared by the following steps:

and B: 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺Mixing the benzoic acid-phenanthroline-europium ternary complex and calcium fluoride, adding the mixture into the modified base solution, stirring and dispersing the mixture uniformly at the temperature of 70 ℃, then preserving the temperature for 25min, adding silicon dioxide, mixing the mixture, preserving the temperature for 3h at the temperature of 70 ℃, and drying the mixture to obtain the modified nano photochromic material.

In the step A, the mixing weight ratio of the lauryl alcohol polyoxyethylene ether, the mixed solvent and the silane coupling agent is 1: 15: 0.8, the mixed solvent consists of isopropanol and ethyl orthosilicate in a weight ratio of 2:1, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane; in the step B, the mixing weight ratio of the nano photochromic material, the modified base solution and the silicon dioxide is 5:10: 4.

The particle size of the prepared modified nano photochromic material is 180 nm.

Example 5

This embodiment differs from embodiment 2 described above in that:

and B: 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺Mixing the benzoic acid-phenanthroline-europium ternary complex and calcium fluoride, adding the mixture into the modified base solution, stirring and dispersing the mixture uniformly at the temperature of 75 ℃, then preserving the heat for 23min, adding silicon dioxide, mixing the mixture, preserving the heat for 2.5h at the temperature of 75 ℃, and drying the mixture to obtain the modified nano photochromic material.

In the step A, the mixing weight ratio of the lauryl alcohol polyoxyethylene ether to the mixed solvent to the silane coupling agent is 1:18:0.6, the mixed solvent consists of isopropanol and tetraethoxysilane in the weight ratio of 2.5:1, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane; in the step B, the mixing weight ratio of the nano photochromic material, the modified base solution and the silicon dioxide is 5:11: 3.

The particle size of the prepared modified nano photochromic material is 200 nm.

Example 6

This embodiment differs from embodiment 2 described above in that:

and B: 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺Mixing the benzoic acid-phenanthroline-europium ternary complex and calcium fluoride, adding the mixture into the modified base solution, stirring and dispersing the mixture uniformly at the temperature of 80 ℃, then preserving the temperature for 20min, adding silicon dioxide, mixing the mixture, preserving the temperature for 2h at the temperature of 80 ℃, and drying the mixture to obtain the modified nano photochromic material.

In the step A, the mixing weight ratio of the lauryl alcohol polyoxyethylene ether to the mixed solvent to the silane coupling agent is 1:20:0.5, the mixed solvent is composed of isopropanol and ethyl orthosilicate in a weight ratio of 3:1, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane; in the step B, the mixing weight ratio of the nano photochromic material, the modified base solution and the silicon dioxide is 5:12: 2.

The particle size of the prepared modified nano photochromic material is 230 nm.

Example 7

This embodiment differs from embodiment 5 described above in that:

the silicon dioxide is pretreated silicon dioxide and comprises the following specific steps:

step (1): calcining silica at 500 deg.C for 60min, and cooling; mixing with 1mol/L nitric acid solution, stirring at 70 deg.C for 6h, filtering, washing with deionized water, vacuum filtering, and drying at 110 deg.C to constant weight;

step (2): performing microwave radiation on the silicon dioxide dried in the step (1) for 3min under the condition that the power is 700W, adding the silicon dioxide subjected to microwave treatment into a sand core funnel, introducing nitrogen for 5h, wherein the nitrogen firstly passes through the bottom of a saturated sodium bromide solution and then passes through the silicon dioxide to obtain microwave silicon dioxide;

and (3): dissolving gamma-aminopropyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane in xylene, stirring in a nitrogen protection atmosphere, adding the microwave silica obtained in the step (2) while stirring, stirring and reacting for 28 hours at the temperature of 75 ℃, filtering, extracting the filtered solid with toluene in a Soxhlet extractor for 20 hours, and then vacuum-drying for 6 hours at the vacuum degree of-0.05 MPa and the temperature of 90 ℃ to obtain the pretreated silica.

In the step (1), the mesh number of the silicon dioxide is 40 meshes, and the specific surface area is 330m²The mixing mass ratio of the silicon dioxide to the nitric acid is 2: 5; in the step (3), the mixing mass ratio of the gamma-aminopropyltriethoxysilane, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the dimethylbenzene is 3: 5:50.

Example 8

This embodiment differs from embodiment 5 described above in that:

step (1): calcining silica at 510 deg.C for 50min, and cooling; mixing with 1.3mol/L nitric acid solution, stirring at 75 deg.C for 5.5h, filtering, washing with deionized water, vacuum filtering, and drying at 115 deg.C to constant weight;

step (2): performing microwave radiation on the silicon dioxide dried in the step (1) for 2.5min under the condition that the power is 750W, adding the silicon dioxide subjected to microwave treatment into a sand core funnel, introducing nitrogen for 5.5h, wherein the nitrogen firstly passes through the bottom of a saturated sodium bromide solution and then passes through the silicon dioxide to obtain microwave silicon dioxide;

and (3): dissolving gamma-aminopropyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane in xylene, stirring in a nitrogen protection atmosphere, adding the microwave silica obtained in the step (2) while stirring, stirring for reaction at 80 ℃ for 26 hours, filtering, extracting the filtered solid with toluene in a Soxhlet extractor for 22 hours, and then vacuum-drying at 95 ℃ under the vacuum degree of-0.08 MPa for 5.5 hours to obtain the pretreated silica.

In the step (1), the mesh number of the silicon dioxide is 50 meshes, and the specific surface area is 340m²The mixing mass ratio of the silicon dioxide to the nitric acid is 2: 8; in the step (3), gamma-aminopropylThe mixing mass ratio of the triethoxy silane, the isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the dimethylbenzene is 3: 6:45.

Example 9

This embodiment differs from embodiment 5 described above in that:

step (1): calcining silica at 520 deg.C for 40min, and cooling; mixing with 1.5mol/L nitric acid solution, stirring at 80 deg.C for 5 hr, filtering, washing with deionized water, vacuum filtering, and drying at 120 deg.C to constant weight;

step (2): performing microwave radiation on the silicon dioxide dried in the step (1) for 2min under the condition that the power is 800W, adding the silicon dioxide subjected to microwave treatment into a sand core funnel, introducing nitrogen for 6h, wherein the nitrogen firstly passes through the bottom of a saturated sodium bromide solution and then passes through the silicon dioxide to obtain microwave silicon dioxide;

and (3): dissolving gamma-aminopropyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane in xylene, stirring in a nitrogen protection atmosphere, adding the microwave silica obtained in the step (2) while stirring, stirring at 83 ℃ for reaction for 24 hours, filtering, extracting the filtered solid with toluene in a Soxhlet extractor for 24 hours, and then vacuum-drying at 100 ℃ under the vacuum degree of-0.12 MPa for 6 hours to obtain the pretreated silica.

In the step (1), the mesh number of the silicon dioxide is 60 meshes, and the specific surface area is 350m²The mixing mass ratio of the silicon dioxide to the nitric acid is 2: 12; in the step (3), the mixing mass ratio of the gamma-aminopropyltriethoxysilane, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the dimethylbenzene is 3: 8:40.

Comparative example 1

This embodiment differs from embodiment 8 described above in that:

in the preparation of the modified nano photochromic material, the step B is to add the silicon dioxide into the modified base solution, then add the nano photochromic material and mix, and the concrete steps are as follows:

and B: adding silicon dioxide into the modified base solution, stirring and dispersing uniformly at 75 ℃, keeping the temperature for 23min, and then adding 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺Mixing the benzoic acid-phenanthroline-europium ternary complex and calcium fluoride to obtain a mixed nano photochromic material, adding the mixed nano photochromic material into a modified base solution containing silicon dioxide, keeping the temperature at 75 ℃ for 2.5 hours, and drying to obtain the modified nano photochromic material.

In the step B, the mixing weight ratio of the mixed nano photochromic material, the modified base solution and the silicon dioxide is 5:11: 3.

Comparative example 2

This embodiment differs from embodiment 8 described above in that:

in the preparation of the modified nano photochromic material, the silane coupling agent added in the step A is a silane coupling agent KH 550.

Comparative example 3

This embodiment differs from embodiment 8 described above in that:

in the preparation of the pretreated silica, a single gamma-aminopropyltriethoxysilane is employed in step (3).

Comparative example 4

This embodiment differs from embodiment 8 described above in that:

in the preparation of the pretreated silica, the single isopropyl dioleate acyloxy (dioctylphosphoroxy) titanate is used in step (3).

Comparative example 5

This embodiment differs from embodiment 7 described above in that:

in the process of preparing the invisible anti-counterfeiting material composition, the phase B is added into the phase A in the third step, and the specific steps are as follows:

step three: stirring the phase A under the condition of the rotating speed of 1300rpm, adding the phase B, adding the CC-08 type fastness reinforcing agent after the phase B is added, uniformly dispersing, and then preserving heat for 2.2 hours at 55 ℃ to prepare the invisible anti-counterfeiting material composition.

A glass block with the thickness of 3cm, the length of 5cm and the width of 5cm is taken, a laser groove with the length of 2cm, the width of 1cm and the depth of 0.5cm is laser-formed on the surface of the glass block under the laser conditions corresponding to the examples 1-9 and the comparative examples 1-5, then the invisible anti-counterfeiting material composition prepared in the examples 1-9 and the comparative examples 1-5 is mixed with a curing agent and is applied to the laser groove, and the anti-counterfeiting glass block test sample with the invisible anti-counterfeiting material is prepared by adopting the type, the addition amount and the curing parameters of the curing agent corresponding to the examples 1-9 and the comparative examples 1-5.

The invisible anti-counterfeiting material compositions prepared in the examples 1 to 9 and the comparative examples 1 to 5 are subjected to fluorescence intensity test, the fluorescence intensity test is carried out by adopting a Tianjin Hongkong Dong F-280 type fluorescence spectrophotometer, the wavelength of ultraviolet light is 360nm, the anti-counterfeiting glass block test sample prepared in the method and the peel strength test between the solidified and molded invisible anti-counterfeiting material and the glass block are carried out according to the GB/T2792-2014 adhesive tape peel strength test method, and the test results are shown as follows:

it can be seen from the above that, in the embodiments 4 to 6, compared with the embodiments 1 to 3, the nano photochromic material is modified, the silica is used as the load, the nano photochromic material is loaded on the silica under the action of the silane coupling agent, and the dispersibility of the nano photochromic material in the system is improved through the dispersibility of the silica, so that the fluorescence performance of the prepared invisible anti-counterfeiting material composition is improved, the adhesion stability of the invisible anti-counterfeiting material composition on the substrate is also improved to a certain extent through the silica, and the peeling strength between the invisible anti-counterfeiting material composition and the substrate is increased.

Compared with the schemes of the embodiments 4 to 6, the schemes of the embodiments 7 to 9 further pretreat the silicon dioxide used for carrying and modifying the nano photochromic material, the gamma-aminopropyltriethoxysilane grafting modification enables the silicon dioxide to be aminopropylated, the bonding property between the silicon dioxide and the high polymer is improved, so that the viscosity of the invisible anti-counterfeiting material composition is increased, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate is grafted and modified, so that the silicon dioxide and the filling material are stably connected, the pretreated silicon dioxide can be stably combined with the high polymer, the filling material and the nano photochromic material, can be uniformly dispersed in the system, and then the stable invisible anti-counterfeiting material composition is obtained, can be stably attached to the surface of the substrate, further improves the peel strength between the substrate and the invisible anti-counterfeiting material composition, and has stable color development and improved fluorescence performance.

Compared with the embodiment 8, in the preparation of the modified nano photochromic material, in the step B, the silicon dioxide is firstly added into the modified base solution, and then the nano photochromic material is added for mixing, so that the fluorescence performance of the test result is obviously reduced, and the peeling strength is slightly reduced.

Compared with the embodiment 8, in the modification process of the nano photochromic material, the silane coupling agent KH550 is adopted to replace gamma-methacryloxypropyltrimethoxysilane, and the fluorescence performance of the test result is obviously reduced, which shows that the gamma-methacryloxypropyltrimethoxysilane adopted by the method has the advantages that silicon hydroxyl on the surface and silicon hydroxyl on the surface of silicon dioxide are dehydrated and condensed to form Si-O-Si bonds and are grafted on the surface of the silicon dioxide, so that the silicon dioxide generates large steric hindrance acting force and good dispersibility, the load of the nano photochromic material is improved, the nano photochromic material is uniformly dispersed, and the fluorescence performance is uniform and stable.

And the comparative examples 3 to 4 adopt a single coupling agent to pretreat the silicon dioxide, and the peel strength of the test result is obviously reduced compared with that of the example 8, which shows that the dispersibility of the silicon dioxide in the anti-counterfeiting material composition and the associativity with materials can be obviously improved and the adhesion stability on the surface of the matrix can be improved by modifying the silicon dioxide by compounding the gamma-aminopropyltriethoxysilane and the isopropyldioleacyloxy (dioctyl phosphoryloxy) titanate.

Compared with the example 8, in the process of preparing the invisible anti-counterfeiting material composition, the phase B is added into the phase A in the step three, so that the glass strength is obviously reduced, and the fluorescence strength is also reduced, probably because the phase A containing the high polymer is added into the phase B of the powder, the system can be uniformly dispersed, the adhesion is better, and the condition of non-uniform dispersion of the powder is likely to occur when the phase B is added into the phase A, so that the adhesion stability of the anti-counterfeiting material composition is influenced.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims

1. A invisible anti-counterfeiting material composition is characterized in that: the feed comprises the following raw materials in parts by weight:

2. The invisible anti-counterfeiting material composition according to claim 1, wherein: the nanometer photochromic material is a modified nanometer photochromic material subjected to load modification treatment, and is prepared by the following steps:

and B: 3-diethylamino-6-methyl-7-phenylaminofluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and Y₂O₂S:Eu³⁺Mixing the benzoic acid-phenanthroline-europium ternary complex and calcium fluoride, adding the mixture into the modified base solution, stirring and dispersing the mixture uniformly at the temperature of 70-80 ℃, then preserving the heat for 20-25min, adding silicon dioxide, mixing, preserving the heat for 2-3h at the temperature of 70-80 ℃, and drying to obtain the modified nano photochromic material.

3. The invisible anti-counterfeiting material composition according to claim 2, wherein: in the step A, the mixing weight ratio of the lauryl alcohol polyoxyethylene ether to the mixed solvent to the silane coupling agent is 1:15-20:0.5-0.8, the mixed solvent consists of isopropanol and ethyl orthosilicate in a weight ratio of 2-3:1, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane; in the step B, the mixing weight ratio of the nano photochromic material, the modified base solution and the silicon dioxide is 5:10-12: 2-4.

4. The invisible anti-counterfeiting material composition according to claim 2, wherein: the silicon dioxide is pretreated silicon dioxide and comprises the following specific steps:

and (3): dissolving gamma-aminopropyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane in xylene, stirring in a nitrogen protection atmosphere, adding the microwave silica obtained in the step (2) while stirring, stirring and reacting for 24-28h at the temperature of 75-83 ℃, filtering, extracting the filtered solid with toluene in a Soxhlet extractor for 20-24h, and then vacuum drying to obtain the pretreated silica.

5. The invisible anti-counterfeiting material composition according to claim 4, wherein: in the step (1), the calcining temperature is 500-520 ℃, and the calcining time is 40-60 min; the concentration of the nitric acid solution is 1-1.5mol/L, and the mixing mass ratio of the silicon dioxide to the nitric acid is 2: 5-12; the microwave power of the microwave treatment in the step (2) is 700-800W, and the microwave time is 2-3 min; in the step (3), the mixing mass ratio of the gamma-aminopropyltriethoxysilane, isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate and the dimethylbenzene is 3: 5-8:40-50, wherein the vacuum drying temperature is 90-100 ℃, and the vacuum drying time is 5-6 h.

6. The invisible anti-counterfeiting material composition according to claim 1, wherein: the particle size of the nano photochromic material is 150-200nm, and the dispersing agent is at least one of polyvinyl alcohol, a dispersing agent BYK-193 and a dispersing agent BYK-185; the filler is a mixture of nano bentonite and calcium carbide in a weight ratio of 3-4: 1; the surfactant is at least one of nonyl phenol polyether-10, polysorbate-20 and coconut diethanolamide.

7. The invisible anti-counterfeiting material composition according to claim 1, wherein: the high polymer is one of polyester resin, polyurethane resin, epoxy resin and alkyd resin; the fastness enhancer is a CC-08 type fastness reinforcing agent; the solvent comprises 2-5 parts by weight of ethylene glycol, 3-4 parts by weight of ethyl acetate and 5 parts by weight of water.

8. A process for preparing the invisible security material composition according to any one of claims 1 to 7, wherein: the method comprises the following steps:

9. Use of the invisible security material composition according to any one of claims 1 to 7, wherein: the invisible anti-counterfeiting material composition can be applied to packaging films, packaging boxes or anti-counterfeiting labels.

10. Use of the invisible security material composition according to any one of claims 1 to 7 in a loading container, characterized in that: the method comprises the following steps: