CN114834172A - Multiple anti-counterfeiting method based on structural color and multiple anti-counterfeiting element - Google Patents
Multiple anti-counterfeiting method based on structural color and multiple anti-counterfeiting element Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
Abstract
The application discloses a multiple anti-counterfeiting method based on structural colors and a multiple anti-counterfeiting element. The anti-counterfeiting method comprises the following steps: forming a photonic crystal layer on the surface of an article to be anti-counterfeit, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under the irradiation of visible light, the first preset pattern is used as a first anti-counterfeit mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are mutually complementary and are jointly used as a second anti-counterfeit mark, and the first reflection wavelength and the second reflection wavelength are different from each other; and applying external stimulus to the photonic crystal layer to enable the first preset pattern and the second preset pattern to be sequentially converted from an invisible state to a visible state so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and after the first anti-counterfeiting mark and the second anti-counterfeiting mark are integrated, the complete encrypted information can be read. The application realizes multiple anti-counterfeiting, increases the imitation difficulty and improves the encryption degree.
Description
Technical Field
The application relates to the technical field of anti-counterfeiting, in particular to a multiple anti-counterfeiting method and a multiple anti-counterfeiting element based on structural colors.
Background
Anti-counterfeiting technology is widely applied to commodities and is used for discriminating whether products are counterfeit or counterfeit. In the prior art, most products are coated with pigments, polymer dots, rare earth metals and the like for anti-counterfeiting, but the problems of poor stability, high cost, high long-term toxicity, easy imitation, low encryption reliability and the like generally exist, and the practical application of the products in the fields of textile clothing and the like is limited.
The responsive photonic crystal structure has the advantages of fastness, environmental protection and the like, and has wide application prospect in the anti-counterfeiting field, then the existing anti-counterfeiting technology usually only has one information encryption, is easy to copy, has low encryption degree, simple and easy-to-break response conditions, still needs a safe and reliable anti-counterfeiting element in the field, cannot be easily copied and is green and environment-friendly.
Disclosure of Invention
An object of the present application is to provide a multiple anti-counterfeiting method based on structural color, so as to solve the technical problems of easy imitation and low encryption degree of the anti-counterfeiting method in the prior art, and simultaneously reduce the production cost and improve the stability and environmental protection performance.
Objects of the present application are not limited to the above objects, and other objects and advantages of the present application, which are not mentioned above, can be understood from the following description and more clearly understood through embodiments of the present application. Further, it is easily understood that the objects and advantages of the present application can be achieved by the features disclosed in the claims and the combinations thereof.
In a first aspect, according to an embodiment of the present application, the present application provides a multiple anti-counterfeiting method based on structural color, including the following steps:
forming a photonic crystal layer on the surface of an article to be anti-counterfeit, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeit mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeit mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
and applying external stimulus to the photonic crystal layer to enable the first preset pattern and the second preset pattern to be sequentially converted from an invisible state to a visible state so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and after the first anti-counterfeiting mark and the second anti-counterfeiting mark are integrated, complete encryption information can be read.
In some of these embodiments, the first reflected wavelength is greater than the second reflected wavelength, and both are less than the wavelength of visible light.
In some of these embodiments, the external stimulus causes the dielectric refractive indices of the first and second photonic crystals to increase such that the first and second reflected wavelengths each increase and in turn equal the wavelength of the visible light.
In some of these embodiments, causing the dielectric refractive indices of the first and second photonic crystals is accomplished by applying a responsive solvent to the photonic crystal layer, the responsive solvent comprising a first responsive solvent and a second responsive solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
In some embodiments, the first photonic crystal and the second photonic crystal are self-assembled from colloidal microspheres, respectively;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
In some of these embodiments, the photonic crystal layer is configured such that the first and second security features are convertible to be invisible under visible light illumination once the external stimulus is removed or an opposite stimulus is applied.
In a second aspect, according to an embodiment of the present application, there is provided a multiple security element based on structural colors, comprising:
the anti-counterfeiting mark comprises a substrate and a photonic crystal layer attached to the surface of the substrate, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeiting mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeiting mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
the first preset pattern and the second preset pattern can be sequentially converted from an invisible state to a visible state through external stimulation so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and complete encryption information can be read after integration.
In some of these embodiments, the first reflected wavelength is greater than the second reflected wavelength, and both are less than the wavelength of visible light.
In some of these embodiments, the external stimulus causes the dielectric refractive indices of the first and second photonic crystals to increase such that the first and second reflected wavelengths each increase and in turn equal the wavelength of visible light.
In some of these embodiments, causing the dielectric refractive indices of the first and second photonic crystals is accomplished by applying a responsive solvent to the photonic crystal layer, the responsive solvent comprising a first responsive solvent and a second responsive solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
In some embodiments, the first photonic crystal and the second photonic crystal are self-assembled from colloidal microspheres, respectively;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
Optionally, the photonic crystal layer is configured such that the first and second security features are convertible to be invisible under irradiation by visible light once the external stimulus is removed or an opposite stimulus is applied.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
the anti-counterfeiting method provided by the embodiment of the application carries out color development through structural color without depending on pigment, and is high in resolution, strong in color fastness, green and environment-friendly; the first preset pattern and the second preset pattern are sequentially converted from the invisible state to the visible state, so that multiple anti-counterfeiting is realized, the imitation difficulty is increased, and the encryption degree is improved.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is a scanning electron microscope photograph of a photonic crystal layer of an embodiment of the present application;
FIG. 2 is a schematic diagram of a reversible imaging process for a security element according to one embodiment of the present application; wherein: 1. applying a first responsive solvent; 2. applying a second responsive solvent; 3. removing the response solvent;
FIG. 3 is a schematic view of a reversible visualization process of a security element according to another embodiment of the present application; wherein: 1. applying a first responsive solvent; 2. applying a second responsive solvent; 3. the response solvent was removed.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
According to a first aspect of the present application, the present application provides a multiple anti-counterfeiting method based on structural color, comprising the following steps:
forming a photonic crystal layer on the surface of an article to be anti-counterfeit, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeit mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeit mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
and applying external stimulus to the photonic crystal layer to enable the first preset pattern and the second preset pattern to be sequentially converted from an invisible state to a visible state so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and after the first anti-counterfeiting mark and the second anti-counterfeiting mark are integrated, complete encryption information can be read.
In this embodiment, the first predetermined pattern is used as the first anti-counterfeit mark to realize the first duplicate anti-counterfeit, and the first predetermined pattern and the second predetermined pattern jointly form the second anti-counterfeit mark to realize the second duplicate anti-counterfeit. Under the natural state, the first anti-counterfeiting mark and the second anti-counterfeiting mark are secret and invisible, namely invisible anti-counterfeiting encryption information is loaded in the photonic crystal layer, when external stimulation is applied to the photonic crystal layer, the first preset pattern and the second preset pattern are visible in sequence, finally the first anti-counterfeiting mark and the second anti-counterfeiting mark are displayed in sequence, and complete encryption information can be read after synthesis, so that double anti-counterfeiting is realized.
It can be understood that the complete anti-counterfeiting encryption information can be composed of a first preset pattern, a second preset pattern and a third preset pattern which are complementary, under the first external stimulation, the first preset pattern is displayed and serves as a first anti-counterfeiting mark, under the second external stimulation, the first preset pattern and the second preset pattern are both displayed and jointly form a second anti-counterfeiting mark, under the third external stimulation, the first preset pattern, the second preset pattern and the third preset pattern are all displayed and jointly form a third anti-counterfeiting mark, so that the first anti-counterfeiting mark, the second anti-counterfeiting mark and the third anti-counterfeiting mark are sequentially displayed, and therefore the invisible encryption information loaded in the photonic crystal layer is read by combining with the three external stimulations, and triple anti-counterfeiting is realized. It can be understood that the complete anti-counterfeiting encryption information can be composed of a first preset pattern, a second preset pattern, a third preset pattern and a fourth preset pattern which are complementary to each other, so that quadruple anti-counterfeiting and the like are formed, and under the condition that the anti-counterfeiting patterns comprise a plurality of photonic crystal structures, counterfeiting and changing of the anti-counterfeiting encryption information are difficult to perform, so that the counterfeiting difficulty is increased, and the anti-counterfeiting effect is improved.
And the light emitted by the photonic crystal layer is different from pigment, and the light selectively reflects visible light with specific wavelength through the Bragg diffraction effect of the periodic arrangement structure of the photonic crystal, so that a three-dimensional structure color is formed. The structural color is the subversion of the traditional pigment dye used in the existing printing, the presented color is not derived from any pigment or dye at all, and the color can not be mixed and reproduced by the conventional chemical pigment, so that the anti-counterfeiting method has certain imitation difficulty and can not be easily imitated, and the anti-counterfeiting method has the advantages of stable property, high color saturation, lasting color, environmental protection and no pollution, and can not be matched by the traditional anti-counterfeiting method.
The term "visible" is meant to include visible patterns when viewed by the naked eye and/or using suitable instrumentation, preferably by the naked eye.
The term "sequentially" means that the first predetermined pattern is first converted from an invisible state to a visible state and then the second predetermined pattern is converted from an invisible state to a visible state; or, the second preset pattern is firstly converted from the invisible state to the visible state, and then the first preset pattern is converted from the invisible state to the visible state. In a specific embodiment of the present application, "sequentially" means that the first predetermined pattern is first converted from an invisible state to a visible state, and then the second predetermined pattern is converted from an invisible state to a visible state, so as to sequentially display the first anti-counterfeit mark and the second anti-counterfeit mark.
Wherein, the photonic crystal layer is formed on the surface of the article to be anti-counterfeiting, and the photonic crystal layer can be formed by applying ink capable of forming the photonic crystal layer to the surface of the article to be anti-counterfeiting by using a method such as spin coating, dip coating, roll coating, silk screen coating, spray coating, spin casting, flow coating, silk screen printing, spraying, drop casting, and the like.
The first preset pattern and the second preset pattern may be a graphic, a letter or a number, and the application is not limited thereto.
Among them, the article to be counterfeit-protected may be a subject article to be protected from forgery and tampering to protect the brand, and may be, for example, a medicine, a toy, a cosmetic, tobacco, alcoholic beverages, clothes, fabric, food, sports goods, shoes, automobile parts, credit cards, silicon chips, and the like, but is not limited thereto.
Further, in some embodiments of the present application, the first reflected wavelength is greater than the second reflected wavelength, and both are less than the wavelength of visible light.
In the embodiment, the first reflection wavelength and the second reflection wavelength are smaller than the wavelength of visible light (380-780nm) so that the first preset pattern and the second preset pattern are invisible under the irradiation of the visible light, wherein the external stimulus is configured to increase the first reflection wavelength and the second reflection wavelength so that the photonic band gaps of the first photonic crystal and the second photonic crystal sequentially enter the visible light range to generate a common structural color, thereby making the first preset pattern and the second preset pattern visible.
Wherein the first reflected wavelength is greater than said second reflected wavelength such that under an external stimulus the first reflected wavelength first increases to equal the wavelength of visible light, the first predetermined pattern is displayed first and the second predetermined pattern is displayed in a subsequent stimulus.
The difference between the first reflected wavelength and the second reflected wavelength may be, for example, 1nm to 200 nm. Specifically, the difference between them may be 50nm to 100nm, and the display of the forgery-preventing mark can be controlled by adjusting the difference between the reflection wavelengths in the above-mentioned ranges. The specific reflection wavelength is not particularly limited. For example, the first reflection wavelength may be 250nm to 300nm, and the second reflection wavelength may be 150nm to 200 nm.
Further, in some embodiments of the present application, the external stimulus causes the dielectric refractive indices of the first and second photonic crystals to increase such that the first and second reflected wavelengths increase respectively and in turn equal to the wavelength of visible light.
The reflection wavelength of the photonic crystal (i.e., the photonic band gap) is determined by the refractive index (or dielectric constant) of the medium and the lattice parameter of the photonic crystal, and it can be known from the modified bragg formula that the central wavelength of the photonic band gap is in positive correlation with the refractive index of the medium, and the reflection wavelength of the photonic crystal can be increased by increasing the refractive index of the medium. The external stimulus of the application is configured to increase the refractive indexes of the first photonic crystal and the second photonic crystal in sequence, so that the photonic band gaps of the first photonic crystal and the second photonic crystal enter the visible light range in sequence, and the first preset pattern and the second preset pattern are displayed in sequence, so that the structure of the photonic crystal does not need to be changed, and the anti-counterfeiting identification is conveniently realized.
The modulation of the refractive index of the medium may be performed by various methods, such as an electric field, a magnetic field, temperature, a chemical solvent, pressure, light irradiation, and the like.
Further, in some embodiments of the present application, the dielectric refractive indices of the first and second photonic crystals are achieved by applying a responsive solvent to the photonic crystal layer, the responsive solvent comprising a first responsive solvent and a second responsive solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
In the present embodiment, the refractive index of the photonic crystal is positively correlated with the refractive index of the crystal and the refractive index of the medium, that is, with the refractive index of the crystal itself and the refractive index of the surrounding environment. In a natural state, taking the first photonic crystal as an example, the surrounding environment is air, and the refractive index of the medium is the refractive index of air(n Air (a) 1.00), when the first response solvent is applied to the photonic crystal layer, the air in the photonic crystal gap becomes the first response solvent with larger refractive index (taking ethanol as an example, n) Ethanol ≈1.36>1.00) and thus the refractive index of the first photonic crystal is increased, thereby increasing the first reflected wavelength into the visible range.
In this embodiment, the first responsive solvent is configured to increase the first reflected wavelength to visible wavelengths and not to increase the second reflected wavelength to visible wavelengths, and the second responsive solvent is configured to increase the second reflected wavelength to visible wavelengths and still maintain the first reflected wavelength within the visible wavelength range. Specifically, after the first response solvent is applied to the photonic crystal layer, since the first reflection wavelength is greater than the second reflection wavelength, and a proper difference exists between the first reflection wavelength and the second reflection wavelength, the first reflection wavelength is increased to be equal to the visible light wavelength, while the second reflection wavelength is increased but still smaller than the visible light wavelength, the first preset pattern is visible, the second preset pattern remains invisible, after the second response solvent is applied to the photonic crystal layer, the second reflection wavelength is further increased to be equal to the visible light wavelength, while the first reflection wavelength is further increased but still stays within the visible light wavelength range, both the first preset pattern and the second preset pattern are visible, and the anti-counterfeiting mark is completely displayed.
The selection of the first response solvent and the second response solvent is related to the specific values of the first reflection wavelength and the second reflection wavelength, and the selection needs to be reasonably selected according to the difference between the first reflection wavelength and the second reflection wavelength and the difference between the first reflection wavelength and the visible light wavelength. In some embodiments, the first response solvent is water, the second response solvent is ethanol, in other embodiments, the first response solvent is water, the second response solvent is glycerol, in still other embodiments, the first response solvent is ethanol, the second response solvent is glycerol, and the refractive index of the first response solvent is smaller than that of the second response solvent, so that the first preset pattern can be displayed first and the second preset pattern can be displayed later, and multiple anti-counterfeiting is achieved.
The anti-counterfeiting method in the embodiment has easy identification, can be conveniently visually identified by using liquid such as water and is nondestructive testing. Wherein, the response solvent is applied to the photonic crystal layer by spraying the response solvent to the photonic crystal layer or dipping the photonic crystal layer into the response solvent.
Further, in some embodiments of the present application, the first photonic crystal and the second photonic crystal are each self-assembled from colloidal microspheres;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
The reflection wavelengths of the first photonic crystal and the second photonic crystal can be obtained by adjusting the type of the colloidal microsphere and adjusting the particle size of the colloidal microsphere in a normal state, wherein the particle size of the colloidal microsphere can be 100-400 nm.
Further, in some embodiments of the present application, the photonic crystal layer is configured such that the first and second security features are convertible to be invisible under irradiation by visible light once the external stimulus is removed or an opposite stimulus is applied.
That is, the display and concealment of the security encryption information of the present application is reversible, such that the security structure formed on the article thereby can be reused multiple times. For example, after applying the response solvent to authenticate the authenticity, the photonic crystal layer may be dried or air-dried, and the crystal medium may be returned to the air again, so that the first predetermined pattern and the second predetermined pattern are changed from the visible state to the invisible state. Or applying another solvent that decreases the refractive index of the response solvent to change the first and second predetermined patterns from the visible state to the invisible state.
Further, the first photonic crystal and the second photonic crystal of the present application may be the same or different in color, and preferably, the colors of the first photonic crystal and the second photonic crystal are different, so as to further increase the difficulty of imitation.
Based on the same inventive concept, in a second aspect of the present application, the present application proposes a multiple security element based on structural color, comprising:
the anti-counterfeiting mark comprises a substrate and a photonic crystal layer attached to the surface of the substrate, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeiting mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeiting mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
the first preset pattern and the second preset pattern can be sequentially converted from an invisible state to a visible state through external stimulation so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and complete encryption information can be read after integration.
The anti-counterfeiting element and the anti-counterfeiting method have corresponding distinguishing technical characteristics, so that the anti-counterfeiting element has the same technical effect, and the details are not repeated.
In this embodiment, the substrate is used to fix the photonic crystal structure. The substrate may be any of a fabric, paper, carbon material, metal foil, thin glass, or plastic substrate.
Further, in some embodiments of the present application, the first reflected wavelength is greater than the second reflected wavelength, and both are less than the wavelength of visible light.
Further, in some embodiments of the present application, the external stimulus causes the dielectric refractive indices of the first and second photonic crystals to increase such that the first and second reflected wavelengths increase respectively and in turn equal to the wavelength of visible light.
Further, in some embodiments of the present application, the dielectric refractive indices of the first and second photonic crystals are achieved by applying a responsive solvent to the photonic crystal layer, the responsive solvent comprising a first responsive solvent and a second responsive solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
Further, in some embodiments of the present application, the first photonic crystal and the second photonic crystal are each self-assembled from colloidal microspheres;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
Illustratively, a first colloidal microsphere dispersion and a second colloidal microsphere dispersion are first prepared. Each dispersion can be prepared by dispersing colloidal microspheres in a solvent. Here, the dispersion liquid is used as a term indicating various states, such as a solution phase, a slurry phase, or a paste phase. At this time, the solvent may use any solvent as long as it can disperse the colloidal microspheres. Secondly, according to the shape of the designed pattern, uniformly spray-printing a first colloidal microsphere dispersion liquid corresponding to a first preset pattern in a corresponding design range on a substrate through an ink-jet printer, and drying the substrate in a drying oven at 40-80 ℃ after spray-printing to form a first photonic crystal; and then, uniformly spraying and printing a second colloidal microsphere dispersion liquid corresponding to a second preset pattern in a corresponding design range on the substrate, and then placing the substrate in an oven at 40-80 ℃ for drying treatment to form a second photonic crystal, thus obtaining the anti-counterfeiting element. Since the first and second predetermined patterns are complementary to each other, their respective perpendicular projections on the substrate do not coincide.
In some embodiments, the first photonic crystal is prepared from a polystyrene colloidal microsphere dispersion (by mass fraction) having a concentration of 10% and the second photonic crystal is prepared from a silica colloidal microsphere dispersion (by mass fraction) having a concentration of 3%.
Further, in some embodiments of the present application, the photonic crystal layer is configured such that once the external stimulus is removed or an opposite stimulus is applied, the first and second security features can be rendered invisible under visible light illumination, thereby allowing repeated and repeated use of the security element of the present application.
Further, in some embodiments of the present application, the security element may further comprise an adhesive portion on the underside of the substrate, in particular on the surface facing away from the photonic crystal layer to be attached. The adhesive portion may comprise an adhesive commonly used in the art to facilitate mounting of the security element to the surface of the article to be secured.
The anti-counterfeiting element can be produced and prepared on a large scale, is low in cost and convenient to pattern, can further meet the personalized customization requirements of the anti-counterfeiting mark, and has uniqueness, fashion and safety.
When the response solvent is applied to the anti-counterfeiting element, the color of the photonic crystal changes instantaneously along with the change of the structural composition (the change of the filling medium), and the response speed is very high. And after the response solvent is removed, the color can be recovered along with the recovery of the photonic crystal structure, and the response solvent can be repeatedly used for many times.
The anti-counterfeiting element has unique color, is flexible and changeable, and the anti-counterfeiting identification method is convenient and diversified, and has obvious anti-counterfeiting effect. Meanwhile, the anti-counterfeiting method has the anti-counterfeiting characteristic of multiple encryption, and is strong in non-replicability, high in encryption degree and high in safety.
The application also provides an anti-counterfeiting component which comprises the anti-counterfeiting element and the response solvent and has a wide application prospect.
Example 1
(1) Preparing a colloidal microsphere dispersion: the monodisperse poly (styrene-methacrylic acid) colloid microspheres with the particle size of 156nm and the monodisperse porous silica colloid microspheres with the particle size of 240nm are dispersed in deionized water, and then are placed in an ultrasonic dispersion machine with the frequency of 120Hz for dispersion for 10 min. Respectively preparing a porous silicon dioxide colloidal microsphere dispersion liquid with the concentration of 3 percent (by mass fraction) and a poly (styrene-methacrylic acid) colloidal microsphere dispersion liquid with the concentration of 10 percent (by mass fraction).
(2) Uniformly spray-printing a monodisperse poly (styrene-methacrylic acid) colloidal microsphere dispersion liquid in a design range of a first preset pattern on a polyester fabric by using an ink-jet printer, and drying the polyester fabric in a drying oven at 60 ℃ after spray-printing to form a first photonic crystal, namely forming the invisible first preset pattern under the irradiation of visible light; and then uniformly spraying and printing the monodisperse porous silica colloidal microsphere dispersion liquid in the design range of a second preset pattern on the polyester fabric, and placing the polyester fabric in a 60 ℃ drying oven for drying after spraying and printing to form a second photonic crystal, namely, a second preset pattern which is invisible under the irradiation of visible light is formed, thus obtaining the anti-counterfeiting element. The colloidal microspheres are observed to be in a regular spherical shape through a scanning electron microscope, the monodispersity is good, the arrangement is compact and regular (figure 1), and the anti-counterfeiting mark is invisible in a normal state.
(3) And selecting the first response solvent as water and the second response solvent as glycerol according to the refractive index and the particle size of the microspheres. After water response is applied to the anti-counterfeiting element, the hidden first preset pattern is displayed, so that the first anti-counterfeiting mark with the shape similar to that of Beidou seven stars is displayed, and the color is purple and bright and full. After the glycerol response is applied, the hidden second preset pattern is displayed and is complementary with the first preset pattern, so that a second anti-counterfeiting mark with a shape similar to that of a small fish is displayed, the first anti-counterfeiting mark and the second anti-counterfeiting mark are sequentially displayed, the complete anti-counterfeiting encryption information is read, the content is 'big dipper seven stars + small fish', the color is blue purple, the color is vivid and flexible, and the identification degree is high (figure 2). Namely, the first response shows the Beidou seven-star, the second response shows the small fish, and the sequentially displayed Beidou seven-star and small fish form double anti-counterfeiting.
(4) After the anti-counterfeiting element is dried, the anti-counterfeiting mark is hidden and invisible.
Example 2
(1) Preparing a colloidal microsphere dispersion: dispersing 154nm monodisperse polystyrene colloid microspheres and 239nm monodisperse porous silicon dioxide colloid microspheres in deionized water, and then placing the mixture in an ultrasonic dispersion machine with the frequency of 120Hz for dispersion for 10 min. Respectively preparing a porous silicon dioxide colloidal microsphere dispersion liquid with the concentration of 3 percent (by mass fraction) and a poly (styrene-methacrylic acid) colloidal microsphere dispersion liquid with the concentration of 10 percent (by mass fraction).
(2) Uniformly spray-printing the monodisperse polystyrene colloidal microsphere dispersion liquid in the design range of a first preset pattern on paper by an ink-jet printer, and drying the paper in a drying oven at 60 ℃ after spray-printing to form a first photonic crystal, namely a first preset pattern which is invisible under the irradiation of visible light; and then uniformly spraying and printing the monodisperse porous silica colloidal microsphere dispersion liquid in the design range of a second preset pattern on the paper, and drying the paper in a drying oven at 60 ℃ after spraying and printing to form a second photonic crystal, namely, a second preset pattern which is invisible under the irradiation of visible light is formed, so as to prepare the anti-counterfeiting element. The colloidal microspheres are observed to be in a regular spherical shape through a scanning electron microscope, the monodispersity is good, the arrangement is compact and regular, and the anti-counterfeiting mark is invisible under a normal state.
(3) And selecting the first response solvent as absolute ethyl alcohol and the second response solvent as glycerol according to the refractive index and the particle size of the microspheres. After absolute ethyl alcohol response is applied to the anti-counterfeiting element, the hidden first preset pattern is displayed, so that a first anti-counterfeiting mark in the shape of '1' is displayed, and the color is purple, bright and full. After the glycerol response is applied, the hidden second preset pattern is displayed and is complementary with the first preset pattern, so that a second anti-counterfeiting mark with the shape of '4' is displayed, the first anti-counterfeiting mark and the second anti-counterfeiting mark are sequentially displayed, the complete anti-counterfeiting encryption information is read, the content is '1 + 4', the color is blue-purple, the color is vivid and flexible, and the identification degree is high (figure 3). Namely, the first response shows 1, the second response shows 4, and the sequentially displayed 1+4 form double anti-counterfeiting.
(4) After the anti-counterfeiting element is dried, the anti-counterfeiting mark is hidden and invisible.
Example 3
(1) Preparing a colloidal microsphere dispersion: dispersing 156nm monodisperse poly (styrene-butyl acrylate-methacrylic acid) colloidal microspheres and 240nm monodisperse porous silicon dioxide colloidal microspheres in deionized water, and then placing the mixture in an ultrasonic disperser with the frequency of 120Hz for dispersing for 10 min. Respectively preparing a porous silicon dioxide colloidal microsphere dispersion liquid with the concentration of 3 percent (by mass fraction) and a poly (styrene-methacrylic acid) colloidal microsphere dispersion liquid with the concentration of 10 percent (by mass fraction).
(2) Uniformly spray-printing the monodisperse poly (styrene-butyl acrylate-methacrylic acid) colloidal microsphere dispersion liquid in the design range of a first preset pattern on the polyester fabric by using an ink-jet printer, and drying the polyester fabric in a drying oven at 60 ℃ after spray-printing to form a first photonic crystal, namely forming the invisible first preset pattern under the irradiation of visible light; and then uniformly spraying and printing the monodisperse porous silica colloidal microsphere dispersion liquid in the design range of a second preset pattern on the polyester fabric, and placing the polyester fabric in a 60 ℃ drying oven for drying after spraying and printing to form a second photonic crystal, namely, a second preset pattern which is invisible under the irradiation of visible light is formed, thus obtaining the anti-counterfeiting element. The colloidal microspheres are observed to be in a regular spherical shape through a scanning electron microscope, the monodispersity is good, the arrangement is compact and regular, and the anti-counterfeiting mark is invisible under a normal state.
(3) And selecting the first response solvent as water and the second response solvent as glycerol according to the refractive index and the particle size of the microspheres. After water response is applied to the anti-counterfeiting element, the hidden first preset pattern is displayed, so that the first anti-counterfeiting mark with the shape similar to that of 'D' is displayed, and the color is purple, bright and full. After the glycerol response is applied, the hidden second preset pattern is displayed and is complementary with the first preset pattern, so that a second anti-counterfeiting mark with the shape similar to 'B' is displayed, the first anti-counterfeiting mark and the second anti-counterfeiting mark are sequentially displayed, the complete anti-counterfeiting encryption information is read, the content is 'D + B', the color is blue-purple, the color is vivid and flexible, and the identification degree is high. Namely, D is displayed under the first re-response, B is displayed under the second re-response, and the sequentially displayed D + B form the double anti-counterfeiting function.
(4) After the anti-counterfeiting element is dried, the anti-counterfeiting mark is hidden and invisible.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the disclosure herein is not limited to the particular combination of features described above, but also encompasses other combinations of features described above or their equivalents without departing from the spirit of the disclosure. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (11)
1. A multiple anti-counterfeiting method based on structural colors is characterized by comprising the following steps:
forming a photonic crystal layer on the surface of an article to be anti-counterfeit, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeit mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeit mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
and applying external stimulus to the photonic crystal layer to enable the first preset pattern and the second preset pattern to be sequentially converted from an invisible state to a visible state so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and after the first anti-counterfeiting mark and the second anti-counterfeiting mark are integrated, complete encryption information can be read.
2. The multiple anti-counterfeiting method according to claim 1, wherein the first reflection wavelength is greater than the second reflection wavelength, and both are less than the wavelength of visible light.
3. The multiple anti-counterfeiting method according to claim 2, wherein the external stimulus causes the dielectric refractive index of the first photonic crystal and the second photonic crystal to increase such that the first reflection wavelength and the second reflection wavelength are respectively increased and are sequentially equal to the wavelength of visible light.
4. The multiple anti-counterfeiting method according to claim 3, wherein the dielectric refractive index of the first photonic crystal and the second photonic crystal is achieved by applying a response solvent to the photonic crystal layer, wherein the response solvent comprises a first response solvent and a second response solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
5. The multiple anti-counterfeiting method according to claim 1, wherein the first photonic crystal and the second photonic crystal are respectively self-assembled by colloidal microspheres;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
6. The multiple anti-counterfeiting method according to any one of claims 1 to 5, wherein the photonic crystal layer is configured such that the first anti-counterfeiting mark and the second anti-counterfeiting mark can be converted to be invisible under irradiation of visible light once the external stimulus is removed or an opposite stimulus is applied.
7. A multiple security element based on structural colors, comprising:
the anti-counterfeiting mark comprises a substrate and a photonic crystal layer attached to the surface of the substrate, wherein the photonic crystal layer at least comprises a first preset pattern and a second preset pattern which are invisible under visible light irradiation, the first preset pattern is used as a first anti-counterfeiting mark and is formed by a first photonic crystal displaying a first reflection wavelength, the second preset pattern is formed by a second photonic crystal displaying a second reflection wavelength, the second preset pattern and the first preset pattern are complementary to each other and are used as a second anti-counterfeiting mark together, and the first reflection wavelength and the second reflection wavelength are different from each other;
the first preset pattern and the second preset pattern can be sequentially converted from an invisible state to a visible state through external stimulation so as to sequentially display the first anti-counterfeiting mark and the second anti-counterfeiting mark, and complete encryption information can be read after integration.
8. The multiple security element of claim 7, wherein the first reflected wavelength is greater than the second reflected wavelength and both are less than the wavelength of visible light.
9. The multiple security element according to claim 8, wherein the external stimulus causes the dielectric refractive index of the first and second photonic crystals to increase such that the first and second reflected wavelengths increase respectively and in turn equal to the wavelength of visible light.
10. The multiple security element according to claim 9, wherein the dielectric refractive indices of the first photonic crystal and the second photonic crystal are achieved by applying a responsive solvent to the photonic crystal layer, the responsive solvent comprising a first responsive solvent and a second responsive solvent;
the first response solvent and the second response solvent are sequentially applied, after the first response solvent is applied, only the first preset pattern is visible, the first anti-counterfeiting mark is completely displayed, after the second response solvent is applied, both the first preset pattern and the second preset pattern are visible, and the second anti-counterfeiting mark is completely displayed;
optionally, the refractive indices of the first and second responsive solvents are different from each other, and the refractive index of the first responsive solvent is smaller than the refractive index of the second responsive solvent;
optionally, the first and second responsive solvents are selected from any one of the following combinations:
water and ethanol, water and glycerol, ethanol and glycerol.
11. The multiple security element of claim 1, wherein the first photonic crystal and the second photonic crystal are each self-assembled from colloidal microspheres;
optionally, the colloidal microspheres constituting the first photonic crystal and the second photonic crystal are each independently selected from any one or more of monodisperse silica, porous silica, polystyrene, poly (styrene-methacrylic acid), poly (styrene-acrylic acid), and poly (styrene-butyl acrylate-methacrylic acid), wherein the refractive index of the colloidal microspheres constituting the first photonic crystal is greater than the refractive index of the colloidal microspheres constituting the second photonic crystal.
Optionally, the photonic crystal layer is configured such that the first and second security features are convertible to be invisible under irradiation by visible light once the external stimulus is removed or an opposite stimulus is applied.
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