CN115976856A

CN115976856A - Method for preparing multiple anti-counterfeiting patterned photonic crystal structure color-producing fabric by screen printing method

Info

Publication number: CN115976856A
Application number: CN202310156385.XA
Authority: CN
Inventors: 邵建中; 陆晓东; 黄海东; 王晓辉; 黄�益
Original assignee: Zhejiang Sci Tech University ZSTU
Current assignee: Zhejiang Sci Tech University ZSTU
Priority date: 2023-02-23
Filing date: 2023-02-23
Publication date: 2023-04-18

Abstract

The invention relates to a method for preparing a color-developing fabric with a multiple anti-counterfeiting patterned photonic crystal structure by a screen printing method, which comprises the following steps: s1, preparing high-quality-fraction nano microsphere color paste and ultraviolet fluorescent printing color paste for structural color generation; s2, scraping and printing the ultraviolet fluorescent printing paste on the surface of the hydrophobic fabric by using a screen printing method to prepare an ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information: s3, scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the S2 by a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern; s4, coating the high-quality-fraction nano microsphere color paste on the surface of the hydrophilic transparent pattern substrate layer obtained in the S3 to prepare a second photonic crystal anti-counterfeiting pattern; and S5, heating the fabric coated with the nano microsphere color paste in the scraping way obtained in the S4 to obtain the multi-anti-counterfeiting patterned color-producing fabric with the photonic crystal structure.

Description

Method for preparing multiple anti-counterfeiting patterned photonic crystal structure color-producing fabric by screen printing method

Technical Field

The invention relates to a preparation method of a photonic crystal anti-counterfeiting pattern, in particular to a method for preparing a multi-anti-counterfeiting patterned photonic crystal structure color-producing fabric by a screen printing method, and belongs to the technical field of printing and dyeing.

Background

Counterfeit products are a long standing and increasingly serious worldwide problem due to the severe negative effects on company reputation, human health and normal economic development sequence. Therefore, it is important to develop a safer, more confidential, green and environmentally-friendly anti-counterfeiting technology to effectively combat counterfeiting.

The Photonic Crystal (PC) is a crystal material formed by arranging two or more media with different dielectric constants in a space according to a certain period, and the application of the Photonic Crystal (PC) in the anti-counterfeiting field is wider due to the characteristic that the unique iridescence effect is endowed by the structure of the photonic crystal. Researchers combine the ultraviolet fluorescence response substance with the photonic crystal and carry out patterning treatment, thereby further strengthening the development of the photonic crystal in the anti-counterfeiting field. Gao et al (GaoZ, chao H, yangD, equivalent. Dual-modular palettenersable dby ultrasound-responsive core-shell colloid spheres [ J]Dyesand pigments,2018, 148.). The Ultraviolet (UV) -responsive colloidal microspheres were prepared using semi-continuous emulsion polymerization. During synthesis, the fluorescent precursor with urethane groups is locally confined in the prepared spherical shell, and then a mask is applied on the surface of the substrate and sprayed to prepare a 2D multicolor PC pattern. Irradiation with ultraviolet light can induce photodecomposition of carbamate groups in the fluorescent precursor and generate amino groups, and the prepared patterned photonic crystals can exhibit fluorescence by treatment with fluorescamine. The novel PC patterns not only show fluorescence, but also have obvious structural colors and multiple anti-counterfeiting effects. Tao et al (TaoJ, luX. Tetraphenylbenzene-modified phosphor organic coating substrate for use in-modificationSound generating devices Physichemistry and engineering industries,2022,655,0927-7757.) emission of organic molecules (AIE) on SiO by Aggregation Induction (AIE) ₂ The surface of the colloidal spheres was modified and then vertically deposited on a masked polyester fabric substrate, modified SiO ₂ The colloid balls are self-assembled into a PC coating. The PC coating not only presents a dazzling structural color due to the Bragg diffraction law, but also presents a pigment color due to the AIE fluorescence effect under ultraviolet irradiation, and has a good anti-counterfeiting effect. The preparation technology modifies the nano-microspheres, so that the microspheres have ultraviolet fluorescence responsiveness, but the preparation process of the microspheres is complicated, and the rapid assembly effect is difficult to realize when the photonic crystal patterns are constructed by a vertical deposition assembly method, so that the anti-counterfeiting products are difficult to realize industrial production. If the ultraviolet fluorescence response substance can be directly combined with the patterned photonic crystal preparation technology, the patterned photonic crystal structure color-generating fabric with multiple anti-counterfeiting functions can be prepared more simply and efficiently, and the application and development of the photonic crystal structure color-generating technology in the fields of textile printing and dyeing and anti-counterfeiting are certainly facilitated.

Disclosure of Invention

The invention aims to provide a method for preparing a multi-anti-counterfeiting patterned photonic crystal structure color-generating fabric by a screen printing method, which can flexibly and quickly print a photonic crystal structure color-generating pattern with multiple anti-counterfeiting effects and high structural stability on the fabric.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a method for preparing a multi-anti-counterfeiting patterned photonic crystal structure color-developing fabric by a screen printing method comprises the following steps:

s1, preparing high-quality-fraction nano microsphere color paste and ultraviolet fluorescent printing color paste for structural color generation

The nano microsphere color paste is formed by mixing nano microsphere dispersion liquid, melanin and surfactant, wherein the mass fraction of nano microspheres in the nano microsphere dispersion liquid is 36-50%, the melanin accounts for 0.04-0.2% of the weight of the nano microsphere dispersion liquid, and the surfactant accounts for 1-3% of the weight of the nano microsphere dispersion liquid;

the nano-microsphere is selected from organic polymerMolecular polymer polymethyl methacrylate (PMMA) nano microspheres, polystyrene (PS) nano microspheres, poly (styrene-methyl methacrylate) (P (St-MMA)), poly (styrene-hydroxyethyl acrylate) (P (St-HEA)), poly (styrene-methacrylic acid) (P (St-MAA)) polystyrene @ polydopamine (PS @ PDA), polystyrene @ silicon dioxide (PS @ SiO 2) ₂ ) Or inorganic Silica (SiO) ₂ ) Any one of the nano-microspheres;

the ultraviolet fluorescent printing paste is formed by mixing an ultraviolet fluorescent response substance, a synthetic thickening agent and soft-segment hard-segment copolymerization type waterborne polyurethane, wherein the using amount of the ultraviolet fluorescent response substance is 6-10% of the weight of the waterborne polyurethane, and the using amount of the synthetic thickening agent is 0.5-1.0% of the weight of the waterborne polyurethane;

the ultraviolet fluorescence response substance is selected from a fluorescent disperse dye, a fluorescent whitening agent or fluorescein;

adding the waterborne polyurethane in the form of aqueous dispersion, wherein the mass fraction is 45-55%;

s2, scraping and printing ultraviolet fluorescent printing paste on the surface of the hydrophobic fabric by using a screen printing method to prepare an ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information;

s3, scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the S2 through a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern;

the paint of the transparent pattern substrate layer is formed by mixing a synthetic thickener, soft-segment hard-segment copolymerization type water-based polyurethane or water-based polyacrylate and a hydrophilic substance, wherein the dosage of the synthetic thickener is 0.5-1.0% of the weight of the water-based polyurethane or water-based polyacrylate, the dosage of the hydrophilic substance is 0.5-2.5% of the weight of the water-based polyurethane or water-based polyacrylate,

the soft-segment hard-segment copolymerization type waterborne polyurethane or waterborne polyacrylate is added in the form of water dispersion with the mass fraction of 45-55%,

the hydrophilic substance is one or a mixture of more of glycerol, ethylene glycol, propylene glycol and urea;

s4, coating the high-quality-fraction nano microsphere color paste on the surface of the hydrophilic transparent pattern substrate layer obtained in the S3 to prepare a second photonic crystal anti-counterfeiting pattern;

and S5, heating the fabric obtained in the step S4, and completing the assembly of the nano microspheres, the activation and migration of the interface molecules of the high molecular layer, the secondary curing in the photonic crystal structure and the stable curing of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Preferably, in S2, the screen printing process is: and scraping and printing twice on a 100-150-mesh screen by using a rubber scraper, drying at 80-90 ℃, and baking at 140-150 ℃ for 1-2min to obtain the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information.

The best choice is as follows: the rubber scraper is used for scraping and printing twice on a 120-mesh screen, drying at 80 ℃ and baking at 140 ℃ for 2min. The ultraviolet fluorescent first anti-counterfeiting pattern under the condition has better uniformity and fineness.

Preferably, in S3, the screen printing process is as follows: and scraping and printing the transparent pattern on a 100-150-mesh screen twice by a rubber scraper, drying at 80-90 ℃, and baking at 120-130 ℃ for 1-2min, wherein the prepared transparent pattern substrate layer is required to completely cover the first anti-counterfeiting pattern.

The best choice is as follows: the rubber scraper is used for scraping and printing twice on a 120-mesh screen, drying at 80 ℃ and baking at 120 ℃ for 1min. The uniformity and fineness of the transparent pattern substrate layer under the condition are better, the surface contact angle is lower, and the hydrophilic performance is better.

Preferably, the diameter of the nano microsphere is 150-350 nm, the sphericity is good, and the monodispersion index is less than 0.08.

Preferably, the heating treatment conditions in S5 are: the temperature is 50-70 deg.C, humidity is 50-70%, and the time is 3-60min.

The best choice is as follows: the temperature is 60 deg.C, humidity is 60%, and the time is 30min. Under the condition, the nano microspheres are directionally arranged under enough thermal driving force, the arrangement time is long, and the assembly regularity is good.

Preferably, the fabric is a blended fabric of one or more of natural fibers or synthetic fibers, the natural fibers comprise cotton, hemp, silk or wool, the synthetic fibers comprise terylene, chinlon, spandex, polypropylene, acrylon, polylactic acid or carbon fibers, and the fabric is subjected to hydrophobic finishing;

the hydrophobic finishing process comprises the following steps: the concentration of the silicon-containing water repellent finishing agent or the fluorine-containing water repellent finishing agent is 4-6% (owf), the bath ratio is 1:15-25, soaking the fabric for 15-20min, drying at 80-90 deg.C, and baking at 140-150 deg.C for 1-2min to obtain the final product.

The best choice is as follows: the fluorine-containing water repellent finishing agent has the concentration of 5% (owf), the bath ratio of 1: soaking the fabric for 18min under the soaking condition of 20 deg.C, squeezing, drying at 90 deg.C, and baking at 140 deg.C for 2min. The fabric treated under the condition has the highest contact angle on the surface and has better hydrophobic property.

Preferably, the soft block and hard block copolymerization type waterborne polyurethane has a hard block selected from one of toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate; the soft segment is a long carbon chain soft substance with crystallization performance, the length of a carbon chain in a repeating unit is more than 4C, and the soft segment is selected from one of poly (1, 4-butanediol adipate), poly (1, 6-hexanediol adipate) and poly (1, 6-hexamethylene-carbonate);

the soft segment and hard segment copolymerization type water-based polyacrylate has the hard segment selected from one of methyl methacrylate, hydroxyethyl methacrylate or methyl acrylate, the soft segment is a long straight chain monomer with more than 4C, and the soft segment is selected from one of butyl acrylate, n-pentyl acrylate, n-hexyl acrylate and isooctyl acrylate.

Preferably, the melanin is one or a mixture of more of carbon black and water-soluble melanin.

Preferably, the surfactant is one or a mixture of several of polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate or ethylene oxide adduct of polypropylene glycol.

Preferably, the synthetic thickener is alkali-resistant and salt-resistant acrylonitrile synthetic thickener, and is selected from the synthetic thickeners for printing paste commonly used in the field, and mainly meets the requirements of alkali resistance and salt resistance.

Preferably, in S1, the components of the nano-microsphere printing paste and the ultraviolet fluorescent printing paste are mixed and then are magnetically stirred for 10min at the speed of 20r/S to be uniformly mixed.

Compared with the prior art, the invention has the beneficial effects that:

1. the multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric prepared by the invention is subjected to selective reflection under sunlight due to the existence of a photonic forbidden band, presents a structural color pattern, changes along with the change of an observation angle, does not have a fluorescent anti-counterfeiting pattern hidden below, and only displays the photonic crystal pattern with obvious angle dependence. Under the irradiation of ultraviolet light, the photonic crystal pattern has no selective reflection of visible light, human eyes feel black, and the fluorescent substance on the pattern at the bottom layer shows obvious fluorescent effect under the action of the ultraviolet light. The method can realize double anti-counterfeiting effects of the iridescent effect pattern of the photonic crystal changing along with the angle under sunlight and the fluorescent pattern displayed under ultraviolet irradiation.

2. In the preparation of the conventional anti-counterfeiting patterned photonic crystal, the nano microspheres need to be modified, so that the microspheres have responsiveness, and the preparation method is complicated. The invention physically combines the anti-counterfeiting fluorescent pattern and the photonic crystal pattern to ensure that the anti-counterfeiting fluorescent pattern and the photonic crystal pattern have multiple anti-counterfeiting effects, and a screen printing method is applied to simply and conveniently print fine patterns, so that the anti-counterfeiting fluorescent pattern with fine coding information can be conveniently obtained, and the patterned photonic crystal can be quickly constructed, so that the patterned photonic crystal with the iridescent effect has the industrialized prospect of large-area, quick and flexible preparation, and the development of the color generation technology of the photonic crystal structure in the anti-counterfeiting field is further promoted.

3. The patterned hydrophilic polymer layer constructed on the surface of the fabric can generate interface activation and interface polymer migration (migration from the substrate layer to the photonic crystal layer) in the assembling process and generate secondary curing in the photonic crystal, so that a ligament effect is played between the structural unit nano microspheres of the photonic crystal, the bearing capacity of the photonic crystal structure to external force (friction, bending, washing and the like) is improved, the stability of the photonic crystal structure is obviously improved, the refractive index difference in the photonic crystal is favorably kept, high-concentration nano microsphere dispersion liquid is used as a blade coating color paste main body, the rapid assembly of the nano microspheres into an ordered photonic crystal structure on the surface of the fabric is favorably realized, the brightness and the saturation of the color of the photonic crystal structure are higher, and the consistency of the high stability and the high saturation of the multicolor anti-counterfeiting photonic crystal structure chromogenic fabric is realized.

Drawings

FIG. 1 is a schematic flow chart of a screen printing method for preparing a multi-anti-counterfeiting patterned photonic crystal structure color-generating fabric in example 1;

FIG. 2 shows the contact angle test results of the hydrophobic finished fabric of example 2 and a hydrophilic patterned substrate layer prepared by a screen printing method;

fig. 3 is a digital picture of the color-producing fabric with a multiple anti-counterfeiting patterned photonic crystal structure prepared in example 3, which is taken in sunlight, wherein a is a sample pattern taken when an angle between an observation angle and a normal is 0 °, b is a sample pattern taken when an angle between an observation angle and a normal is 30 °, and c is a sample pattern taken when an angle between an observation angle and a normal is 60 °;

FIG. 4 is a digital photograph of the multiple anti-counterfeiting patterned photonic crystal structure color-producing fabric prepared in example 4 taken under ultraviolet light;

FIG. 5 shows the reflectivity curve (a) and SEM image (b) of the multiple anti-counterfeiting patterned photonic crystal prepared in example 5;

FIG. 6 shows the results of the multi-fold test of the color-producing fabric with a multiple anti-counterfeit patterned photonic crystal structure prepared in example 6;

FIG. 7 is a digital photograph of a multiple anti-counterfeiting patterned photonic crystal structure color-producing fabric prepared by adding 2.0wt% of an ultraviolet fluorescence responsive substance under ultraviolet light in comparative example 1;

FIG. 8 is a digital photograph of comparative example 2 after using 28wt% nanoparticle dispersion as a knife coating color paste;

FIG. 9 is a digital photograph of comparative example 3, in which 56wt% of nano-microsphere dispersion was used as a coating color paste;

fig. 10 is a result of multi-bending test of the multi-anti-counterfeiting patterned photonic crystal structure color-producing fabric prepared without adding a high molecular polymer to the hydrophilic pattern substrate layer of comparative example 4.

Detailed Description

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The present invention will now be further described with reference to specific examples, which are intended to be illustrative only and not to be limiting. The test samples and test procedures used in the following examples include the following (generally, according to the conventional conditions or according to the conditions recommended by a reagent company if the specific conditions of the experiment not specified in the examples; reagents, consumables and the like used in the following examples are commercially available without specific description).

The reagent sources in the following examples:

hydrophobic finishing agent: fluorine-containing water repellent finishing agent, silicon-containing water repellent finishing agent, zhejiang chemical industries, ltd; (some are listed, but not limited to the above products).

Colloidal nanoparticle dispersion liquid, self-made in laboratories, taking the preparation method of PS nanoparticles as an example: 1000g of deionized water, 450g of styrene (St) were charged into a 3000mL four-necked round-bottomed flask with mechanical stirring and condensation, followed by 0.75g of Sodium Dodecyl Sulfate (SDS) with a stirring speed of 350rpm, and 1.05g of potassium persulfate was dissolved in 50mL of deionized water and added to the four-necked flask when the temperature was raised to 85 ℃. The whole reaction system is carried out in the nitrogen atmosphere for 4-5h. The 30wt% nanoparticle dispersion liquid synthesized above was further evaporated by a rotary evaporator. Filtering the obtained dispersion liquid by using a 200-mesh nylon net to finally obtain the nano microsphere dispersion liquid with the concentration of 36-46 wt%.

Ultraviolet fluorescence responsive substance: rhodamine B, fluorescein, shanghai yi chemico technologies ltd; disperse fluorescent red G, disperse fluorescent orange 2GFL, disperse fluorescent yellow 10GN, disperse fluorescent green 5G, zhejiang gihua group ltd; fluorescent whitening agent CPD-A, tianjin Yudu science and technology development Co., ltd; (some are listed, but not limited to the above products).

Soft segment and hard segment copolymerized polyacrylic acid: waterborne polyacrylate, model P1907, model P3904, model P3902s, and the like, mitsubishi gmbh; soft segment and hard segment copolymerized polyurethane: aqueous polyurethane, type PUE1650, type PUE-2013, type PUE1401, etc., shanghai seishi polymer materials ltd (listed, but not limited to the above products). The soft-segment and hard-segment copolymerization type waterborne polyurethane or waterborne polyacrylate is added in the form of aqueous dispersion.

The invention relates to a large-area preparation method of soft-segment and hard-segment copolymerization type water-based polyacrylate or polyurethane, in particular to a large-area preparation method of a high-stability and high-saturation photonic crystal structure color-generating fabric of CN114164661A in China, and a photonic crystal structure color-generating fabric of CN112323495A and a preparation method thereof.

Example 1

A method for preparing a multiple anti-counterfeiting patterned photonic crystal structure color-producing fabric by a screen printing method comprises the following specific steps:

(1) Preparing high-quality-fraction nano microsphere color paste and ultraviolet fluorescent printing color paste for structural color generation:

mixing PS nano microsphere dispersion with the particle size of 232nm (the mass fraction of PS nano microspheres is 36 wt%), carbon black accounting for 0.04% of the weight of the nano microsphere dispersion and polyoxyethylene sorbitan fatty acid ester accounting for 1%, and then magnetically stirring at the speed of 20r/s for 10min to uniformly mix the mixture for later use;

mixing the waterborne polyurethane PUE1401 dispersion (the mass fraction of the waterborne polyurethane is 50wt percent) with rhodamine B accounting for 6.0 percent of the weight of the waterborne polyurethane and 0.5 percent of synthetic thickener, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method, so that the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information is easily prepared: firstly, the cotton fabric is subjected to hydrophobic finishing, and the concentration of the fluorine-containing water repellent finishing agent is 4 percent

(owf), bath ratio 1:25, soaking the fabric for 20min under the soaking condition, drying the fabric by squeezing, drying the fabric at 80 ℃, and baking the fabric for 1min at 140 ℃ to obtain the strongly hydrophobic fabric;

scraping and printing ultraviolet fluorescent printing paste on the surface of the cotton fabric by a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 10 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing a hydrophilic coating on the surface of the cotton fabric by using a screen printing method, heating and curing to form a film to obtain a fabric with a hydrophilic polymer layer transparent pattern on the surface, wherein the coating amount is 10 g/square meter (dry weight);

the hydrophilic coating is prepared by mixing soft-segment hard-segment copolymerization type waterborne polyacrylate (P1907) and hydrophilic substance (glycerol), wherein the dosage of the hydrophilic substance is 0.6wt% of the solid content of the waterborne polyacrylate in the waterborne polyacrylate emulsion (namely aqueous dispersion liquid) (the same below),

(4) Coating the high-quality-fraction nano microsphere color paste on the surface of the hydrophilic transparent pattern substrate layer obtained in the step S3 to prepare a second photonic crystal anti-counterfeiting pattern;

(5) And (3) placing the coated fabric in an environment with the temperature of 50 ℃ and the humidity of 50% for treating for 60min to complete the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure, thereby obtaining the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Example 2

mixing a PMMA nano microsphere dispersion liquid with the particle size of 310nm (the mass fraction of PMMA nano microspheres is 38 wt%), carbon black accounting for 0.06% of the weight of the nano microsphere dispersion liquid and fatty acid polyoxyethylene ester accounting for 1.5%, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

mixing the waterborne polyurethane PUE1650 dispersion liquid (the mass fraction of the waterborne polyurethane is 50wt percent), fluorescein accounting for 7.0 percent of the weight of the waterborne polyurethane and a synthetic thickener accounting for 0.6 percent of the weight of the waterborne polyurethane, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method, so that the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information is easily prepared: firstly, carrying out hydrophobic finishing on the polyester fabric, wherein the concentration of the fluorine-containing water repellent finishing agent is 5 percent

(owf), bath ratio 1: dipping the fabric for 18min under the dipping condition of 20 ℃, squeezing, drying at 90 ℃, and baking for 2min at 140 ℃ to obtain the strongly hydrophobic fabric;

printing ultraviolet fluorescent printing paste on the surface of the polyester fabric by a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 12 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 12 g/square meter (dry weight);

the hydrophilic coating is formed by mixing soft-segment hard-segment copolymerization type water-based polyacrylate (P3904) and a hydrophilic substance (ethylene glycol), wherein the amount of the hydrophilic substance is 1.0 percent of the mass of the water-based polyacrylate,

(5) And (3) placing the coated fabric in an environment with the temperature of 50 ℃ and the humidity of 60% for processing for 45min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Example 3

A method for preparing a color-producing fabric with a multiple anti-counterfeiting patterned photonic crystal structure by a screen printing method comprises the following specific steps:

mixing PS @ PDA nano-microsphere dispersion with the particle size of 278nm (the mass fraction of PS @ PDA nano-microspheres is 40 wt%), carbon black accounting for 0.02% of the weight of the nano-microsphere dispersion and fatty alcohol-polyoxyethylene ether accounting for 1.8%, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

mixing the aqueous polyurethane PUE-2013 dispersion (the mass fraction of the aqueous polyurethane is 50 wt%), dispersed fluorescent red G accounting for 8.0% of the weight of the aqueous polyurethane and 0.7% of synthetic thickening agent, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the components for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method, so that the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information is easily prepared: firstly, carrying out hydrophobic finishing on the polyester-polyurethane blended fabric, wherein the concentration of a fluorine-containing water repellent finishing agent is 6% (owf), the bath ratio is 1:15 for 16min, squeezing, drying at 80 ℃, and baking at 140 ℃ for 1min to obtain the strongly hydrophobic fabric;

scraping and printing ultraviolet fluorescent printing paste on the surface of the polyester/polyurethane blended fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 15 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of the polyester/polyurethane blended fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 15 g/square meter (dry weight);

the hydrophilic coating is formed by mixing soft-segment hard-segment copolymerization type water-based polyacrylate (P3902 s) and a hydrophilic substance (propylene glycol), wherein the amount of the hydrophilic substance is 1.4 percent of the mass of the water-based polyacrylate,

(5) And (3) placing the coated fabric in an environment with the temperature of 60 ℃ and the humidity of 60% for processing for 30min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Example 4

PS @ SiO with particle size of 256nm ₂ Nano microsphere dispersion (PS @ SiO) ₂ 46wt% of nano microspheres), carbon black accounting for 0.10% of the weight of the nano microsphere dispersion liquid and fatty acid methyl ester ethoxylate accounting for 2.0%, and then uniformly mixing the mixture through magnetic stirring for 10min at the speed of 20r/s for later use;

mixing the waterborne polyurethane PUE1650 dispersion liquid (the mass fraction of the waterborne polyurethane is 50wt percent) with the dispersed fluorescent orange 2GFL accounting for 9.0 percent of the weight of the waterborne polyurethane and 0.8 percent of synthetic thickener, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method to easily prepare an ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information: firstly, carrying out hydrophobic finishing on polyester real silk fabric, wherein the concentration of a silicon-containing water repellent finishing agent is 4% (owf), the bath ratio is 1:25, soaking the fabric for 19min under the soaking condition, drying the fabric by squeezing, drying the fabric at 90 ℃, and baking the fabric for 1min under the temperature of 140 ℃ to obtain the strongly hydrophobic fabric;

scraping and printing ultraviolet fluorescent printing paste on the surface of a real silk fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 15 g/square meter (dry weight);

(3) And (3) scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step (2) by a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of a real silk fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 15 g/square meter (dry weight);

the hydrophilic coating is prepared by mixing soft-segment hard-segment copolymerization type waterborne polyurethane (PUE 1650) and hydrophilic substances (urea), wherein the amount of the hydrophilic substances is 1.8 percent of the mass of the high molecular polymer,

(5) And (3) placing the coated fabric in an environment with the temperature of 60 ℃ and the humidity of 70% for processing for 25min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Example 5

mixing a P (St-HEA) nanoparticle dispersion liquid (the mass fraction of P (St-HEA) nanoparticles is 44 wt%) with a dispersion liquid of P (St-HEA) nanoparticles, wherein the dispersion liquid comprises carbon black accounting for 0.16% of the weight of the dispersion liquid and ethylene oxide adduct of polypropylene glycol accounting for 2.2% of the weight of the dispersion liquid, and then magnetically stirring at a speed of 20r/s for 10min to uniformly mix the mixture for later use;

mixing the aqueous polyurethane PUE1401 dispersion (the mass fraction of the aqueous polyurethane is 50wt percent) with the dispersed fluorescent yellow 10GN accounting for 9.0 percent of the weight of the aqueous polyurethane and 0.9 percent of synthetic thickener, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method, so that the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information is easily prepared: firstly, carrying out hydrophobic finishing on the polyester fabric, wherein the concentration of the silicon-containing hydrophobic finishing agent is 5 percent

(owf), bath ratio 1: dipping the fabric for 17min under the dipping condition of 20 ℃, squeezing, drying at 80 ℃, and baking for 2min at 140 ℃ to obtain the strongly hydrophobic fabric;

scraping and printing ultraviolet fluorescent printing paste on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 18 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 18 g/square meter (dry weight);

the hydrophilic coating is formed by mixing soft-segment hard-segment copolymerization type waterborne polyurethane (PUE-2013) and a hydrophilic substance (ethylene glycol), wherein the using amount of the hydrophilic substance is 2.0 percent of the mass of the high molecular polymer,

(5) And (3) placing the coated fabric in an environment with the temperature of 70 ℃ and the humidity of 70% for processing for 5min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Example 6

mixing P (St-MMA) nano microsphere dispersion liquid (P (St-MMA) nano microsphere mass fraction is 42 wt%) with 292nm particle size, carbon black accounting for 0.18% of nano microsphere dispersion liquid weight and fatty acid methyl ester ethoxylate accounting for 2.5% of nano microsphere dispersion liquid weight, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

mixing the aqueous polyurethane PUE-2013 dispersion (the mass fraction of the aqueous polyurethane is 50 wt%), a fluorescent whitening agent CPD-A accounting for 10.0% of the weight of the aqueous polyurethane and a synthetic thickener accounting for 1.0% of the weight of the aqueous polyurethane, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the aqueous polyurethane and the fluorescent whitening agent CPD-A for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method, so that the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information is easily prepared: firstly, carrying out hydrophobic finishing on the polyester fabric, wherein the concentration of the silicon-containing hydrophobic finishing agent is 6 percent

(owf), bath ratio 1:15 for 15min, squeezing, drying at 90 ℃, and baking at 140 ℃ for 1min to obtain a strongly hydrophobic fabric;

scraping and printing ultraviolet fluorescent printing paste on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 20 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: : scraping and printing hydrophilic coating on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 20 g/square meter (dry weight);

the hydrophilic coating is prepared by mixing soft-segment hard-segment copolymerization type waterborne polyurethane (PUE 1401) and a hydrophilic substance (glycerol), wherein the amount of the hydrophilic substance is 2.2 percent of the mass of the high molecular polymer,

(5) And (3) placing the coated fabric in an environment with the temperature of 70 ℃ and the humidity of 70% for treatment for 7min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Fig. 1 is a schematic flow chart of a screen printing method for preparing a multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric in embodiment 1, and the flow chart can be used for simply and rapidly preparing the multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric.

Fig. 2 is a contact angle test result of the fabric after the hydrophobic finishing in example 2 and the hydrophilic pattern substrate layer prepared by the screen printing method, as shown in fig. 2, the fabric surface has a strong hydrophobic property (contact angle: 135.8 °) by dipping the fabric with the hydrophobic finishing agent and heat-treating for a short time, the polymer layer transparent pattern scratched by the screen printing method has a good hydrophilic property (contact angle: 47.5 °), and it is verified that both the hydrophobic fabric and the hydrophilic polymer layer prepared in examples 1 to 6 can achieve the above effects.

Fig. 3 is a digital picture of the multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric prepared in example 3 taken under sunlight, the prepared structure color-generating pattern is uniform in color and free of defects, and presents different structure colors at different angles to show an iridescence effect, and the structure color-generating patterns prepared in examples 1 to 6 all present obvious angle dependence, namely the iridescence effect.

Fig. 4 is a digital picture of the color-producing fabric with the multiple anti-counterfeiting patterned photonic crystal structure prepared in example 4, which is photographed under ultraviolet light, the photonic crystal on the prepared maple leaf pattern has no selective reflection of green light, and is perceived as black by human eyes, while the fluorescent substance on the two-dimensional code pattern shows an obvious fluorescent effect under the action of ultraviolet light, and can be effectively scanned by a mobile phone, and the ultraviolet fluorescent anti-counterfeiting patterns prepared in examples 1 to 6 can achieve the above effects.

Fig. 5 is a reflectance curve of the photonic crystal prepared in example 5, as shown in fig. 5, the reflectance peak is high and narrow, and the SEM image also shows that the arrangement regularity of the nanospheres is high, which proves that the structural color brightness and saturation are high, and it is verified that the photonic crystals prepared in examples 1 to 6 have high brightness and saturation.

The patterned photonic crystal structure color-producing fabric prepared in example 6 was bent 5 to 6 times. Fig. 6 is a test result of multiple bending of the colored fabric with the patterned photonic crystal structure, and the photonic crystal is not damaged after the multiple bending, which proves that the colored fabric with the patterned photonic crystal structure has excellent structural stability.

Comparative example 1

mixing PS nanometer microsphere dispersion with particle diameter of 232nm (mass fraction of PS nanometer microsphere is 36 wt%), carbon black accounting for 0.04 wt% of nanometer microsphere dispersion, and polyoxyethylene sorbitan fatty acid ester accounting for 1 wt%, after mixing, stirring the mixture for 10min by magnetic force at the speed of 20r/s to ensure that the mixture is uniformly mixed for later use;

mixing the waterborne polyurethane PUE1401 dispersion (the mass fraction of the waterborne polyurethane is 50wt percent) with rhodamine B accounting for 2.0 percent of the weight of the waterborne polyurethane and 0.5 percent of synthetic thickener, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of the cotton fabric by using a screen printing method, heating and curing to form a film to obtain a fabric with a hydrophilic polymer layer transparent pattern on the surface, wherein the coating amount is 10 g/square meter (dry weight);

the hydrophilic coating is prepared by mixing soft-segment hard-segment copolymerization type waterborne polyacrylate (P1907) and hydrophilic substance (glycerol), wherein the dosage of the hydrophilic substance is 0.6wt% of the solid content of the waterborne polyacrylate in a waterborne polyacrylate emulsion (namely a water dispersion liquid) (the same applies below),

(5) And (3) placing the coated fabric in an environment with the temperature of 50 ℃ and the humidity of 50% for treating for 60min to complete the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure, thereby obtaining the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric. A

Comparative example 2

mixing a PMMA (polymethyl methacrylate) nano microsphere dispersion liquid with the grain diameter of 310nm (the mass fraction of PMMA nano microspheres is 28 wt%), carbon black accounting for 0.06% of the weight of the nano microsphere dispersion liquid and fatty acid polyoxyethylene ester accounting for 1.5% of the weight of the nano microsphere dispersion liquid, and then magnetically stirring for 10min at the speed of 20r/s to uniformly mix the mixture for later use;

scraping and printing ultraviolet fluorescent printing paste on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 12 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: : scraping and printing hydrophilic coating on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 12 g/square meter (dry weight);

Comparative example 3

mixing P (St-MMA) nano microsphere dispersion liquid with the particle size of 292nm (the mass fraction of P (St-MMA) nano microspheres is 56 wt%), carbon black accounting for 0.18% of the weight of the nano microsphere dispersion liquid and fatty acid methyl ester ethoxylate accounting for 2.5%, and then magnetically stirring at the speed of 20r/s for 10min to uniformly mix the mixture for later use;

(2) The ultraviolet fluorescent printing paste is printed on the surface of the hydrophobic fabric by a screen printing method to easily prepare an ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information: firstly, carrying out hydrophobic finishing on the polyester fabric, wherein the concentration of the silicon-containing hydrophobic finishing agent is 6 percent

printing ultraviolet fluorescent printing paste on the surface of the polyester fabric by a screen printing method, heating and curing to form a film to obtain the fabric with the ultraviolet fluorescent anti-counterfeiting pattern on the surface, wherein the coating amount is 20 g/square meter (dry weight);

(3) Scraping and printing the slurry on the surface of the hydrophobic fabric with the ultraviolet fluorescent first anti-counterfeiting pattern obtained in the step S2 by using a screen printing method to prepare a hydrophilic transparent pattern substrate layer and completely cover the ultraviolet fluorescent first anti-counterfeiting pattern: scraping and printing hydrophilic coating on the surface of the polyester fabric by using a screen printing method, heating and curing to form a film to obtain the fabric with the surface provided with the hydrophilic polymer layer transparent pattern, wherein the coating amount is 20 g/square meter (dry weight);

(5) And (3) placing the coated fabric in an environment with the temperature of 70 ℃ and the humidity of 70% for treatment for 7min, and completing the assembly of the nano microspheres, the interface molecule activation and migration of the polymer layer on the surface of the fabric and the stabilization of the photonic crystal structure to obtain the multicolor fabric with the multiple anti-counterfeiting patterned photonic crystal structure.

Comparative example 4

the hydrophilic coating is formed by mixing conventional screen printing paste and hydrophilic substances (glycerol), wherein the consumption of the hydrophilic substances is 2.2 percent of the printing paste,

(5) And (3) placing the coated fabric in an environment with the temperature of 70 ℃ and the humidity of 70% for treatment for 7min, and finishing the assembly of the nano microspheres and the stabilization of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure chromogenic fabric.

Fig. 7 is a digital picture of a color-developing fabric with a multiple anti-counterfeiting patterned photonic crystal structure prepared by screen printing of comparative example 1 (compared with example 1) taken under ultraviolet light, as can be seen from fig. 7, the addition amount of ultraviolet fluorescence response substances is small, and under the irradiation of ultraviolet light, the definition of a fluorescence pattern is poor, so that the anti-counterfeiting effect is affected.

FIG. 8 is a digital photo of a multi-anti-counterfeiting patterned photonic crystal structure color-generating fabric prepared by screen printing of comparative example 2 (compared with example 2), and it can be seen from FIG. 8 that when the nanoparticle dispersion liquid with lower solid content is used as the doctor-blade coating color paste, the color brightness and saturation of the prepared structural color-generating pattern are lower.

Fig. 9 is a digital photo of a color-producing fabric with a multiple anti-counterfeiting patterned photonic crystal structure prepared by screen printing of comparative example 3 (compared with example 6), and it can be seen from fig. 9 that when a nanoparticle dispersion with a higher solid content is used as a doctor-blade coating color paste, the color brightness and saturation of the prepared color-producing pattern with a structure are better, but the pattern is easy to generate obvious cracks and has slightly poor definition of the outline due to a larger number of stacked layers of the ordered structure of the photonic crystal (see fig. 9).

Fig. 10 is an optical photograph of the multi-anti-counterfeiting patterned photonic crystal structure yarn dyed fabric prepared in comparative example 4 (compared with example 6) in which the hydrophilic pattern substrate layer is not added with the high molecular polymer after being bent for multiple times, and it can be seen that the structural stability is poor and the photonic crystal is easy to be irreversibly damaged under the action of strong external force.

In conclusion, the multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric prepared by the invention performs selective reflection under sunlight due to the existence of photon forbidden bands, the color changes along with the change of an observation angle, a fluorescent anti-counterfeiting pattern hidden below does not appear, and only a photonic crystal pattern with obvious angle dependence is displayed. Under the irradiation of ultraviolet light, no visible light is selectively reflected on the photonic crystal pattern, human eyes feel black, and the fluorescent substance on the pattern at the bottom layer shows an obvious fluorescent effect under the action of the ultraviolet light, so that the double anti-counterfeiting effect of displaying the fluorescent pattern under the action of the iridescence effect of the photonic crystal and the ultraviolet light irradiation is realized. By the screen printing method, fine patterns can be simply and conveniently printed, so that anti-counterfeiting fluorescent patterns with fine coding information can be conveniently obtained, and patterned photonic crystals can be quickly constructed. By constructing the water-based polyurethane or polyacrylate high molecular polymer receiving and stabilizing layer, the structural stability and structural color durability of the multi-anti-counterfeiting patterned photonic crystal structure color-producing fabric are improved.

The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The method for preparing the multiple anti-counterfeiting patterned photonic crystal structure color-generating fabric by using the screen printing method provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims

1. A method for preparing a multi-anti-counterfeiting patterned photonic crystal structure color-producing fabric by a screen printing method is characterized by comprising the following steps:

the nano-microsphere is selected from organic high-molecular polymer polymethyl methacrylate (PMMA) nano-microsphere, polystyrene (PS) nano-microsphere, poly (styrene-methyl methacrylate) (P (St-MMA)), poly (styrene-hydroxyethyl acrylate) (P (St-HEA)), poly (styrene-methacrylic acid) (P (St-MAA)) polystyrene @ polydopamine (PS @ PDA), polystyrene @ silicon dioxide (PS @ SiO) ₂ ) Or inorganic Silica (SiO) ₂ ) Any one of the nano-microspheres;

the ultraviolet fluorescent printing paste is formed by mixing ultraviolet fluorescent response substances, synthetic thickening agents and soft-segment hard-segment copolymer type waterborne polyurethane, wherein the using amount of the ultraviolet fluorescent response substances is 6-10% of the weight of the waterborne polyurethane, and the using amount of the synthetic thickening agents is 0.5-1.0% of the weight of the waterborne polyurethane;

the ultraviolet fluorescence response substance is selected from fluorescent disperse dyes, fluorescent whitening agents or fluorescein;

the soft-segment and hard-segment copolymerization type waterborne polyurethane is added in the form of aqueous dispersion, and the mass fraction is 45-55%;

the slurry of the transparent pattern substrate layer is formed by mixing a synthetic thickener, soft-segment hard-segment copolymerization type water-based polyurethane or water-based polyacrylate and a hydrophilic substance, wherein the dosage of the synthetic thickener is 0.5-1.0% of the weight of the water-based polyurethane or water-based polyacrylate, the dosage of the hydrophilic substance is 0.5-2.5% of the weight of the water-based polyurethane or water-based polyacrylate,

adding soft-segment hard-segment copolymerization type waterborne polyurethane or waterborne polyacrylate in the form of aqueous dispersion, wherein the mass fraction is 45-55%;

and S5, heating the fabric obtained in the step S4, and completing the assembly of the nano microspheres, the activation and the migration of the interface molecules of the high polymer layer, the secondary curing in the photonic crystal structure and the stable curing of the photonic crystal structure to obtain the multi-anti-counterfeiting patterned photonic crystal structure color-developing fabric.

2. The method of claim 1, wherein: in S2, the screen printing process comprises the following steps: and scraping and printing the rubber scraper twice on a 100-150-mesh screen, drying at 80-90 ℃, and baking at 140-150 ℃ for 1-2min to obtain the ultraviolet fluorescent first anti-counterfeiting pattern with anti-counterfeiting information.

3. The method of claim 1, wherein: in S3, the screen printing process comprises the following steps: and scraping and printing the transparent pattern on a 100-150-mesh screen twice by a rubber scraper, drying at 80-90 ℃, and baking at 120-130 ℃ for 1-2min, wherein the prepared transparent pattern substrate layer is required to completely cover the first anti-counterfeiting pattern.

4. The method of claim 1, wherein: the diameter of the nano microsphere is 150-350 nm, the sphericity is good, and the monodispersion index is less than 0.08.

5. The method of claim 1, wherein: the heating treatment conditions in S5 are as follows: the temperature is 50-70 deg.C, humidity is 50-70%, and the time is 3-60min.

6. The method of claim 1, wherein: the fabric is a blended fabric of one or more of natural fibers or synthetic fibers, the natural fibers comprise cotton, hemp, silk or wool, the synthetic fibers comprise terylene, chinlon, spandex, polypropylene, acrylic fibers, polylactic acid or carbon fibers, and the fabric is subjected to hydrophobic finishing;

7. The method of claim 1, wherein: the soft segment and hard segment copolymerization type waterborne polyurethane has the advantages that the hard segment is selected from one of toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate; the soft segment is a long carbon chain soft substance with crystallization performance, the length of a carbon chain in a repeating unit is more than 4C, and the soft segment is selected from one of poly-1, 4-butanediol adipate, poly-1, 6-hexanediol adipate and poly-1, 6-hexamethylene-carbonate;

8. The method of claim 1, wherein: the melanin is one or a mixture of more of carbon black and water-soluble melanin.

9. The method of claim 1, wherein: the surfactant is one or a mixture of more of polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether, fatty acid-polyoxyethylene ester, fatty acid methyl ester ethoxylate or ethylene oxide adduct of polypropylene glycol.

10. The method of claim 1, wherein: in S1, the components of the nano microsphere printing paste and the ultraviolet fluorescent printing paste are mixed and then are magnetically stirred for 10min at the speed of 20r/S to be uniformly mixed.