Application of self-repairing, anti-fog and anti-frost light-transmitting coating in anti-counterfeiting and anti-counterfeiting product

Abstract

The invention provides application of an anti-fog and anti-frost high-light-transmittance coating with self-repairing performance in anti-counterfeiting and an anti-counterfeiting product. The anti-counterfeiting product comprises a solid substrate; the first anti-counterfeiting coating covers at least one part of the surface of the solid substrate and is formed by an anti-fog and anti-frost high-light-transmittance coating with self-repairing performance. The cross-linking is controlled by optimizing the ratio of the amount of substance of hydroxyl in the polymer containing hydroxyl in the main chain or side chain to the amount of substance of the organosilane reagent serving as the cross-linking agent and the polymer containing carboxyl in the main chain or side chain; a cross-linked transparent coating with self-repairing performance, water resistance, long-acting fog resistance, frost resistance and high light transmittance is obtained on a solid substrate by adopting a coating method, and the transparent coating is applied to the anti-counterfeiting field and is directly used as an anti-counterfeiting coating; therefore, the application of the long-acting anti-fog and anti-frost high-light-transmittance coating with the self-repairing performance in the anti-counterfeiting field is developed, and the coating is particularly suitable for anti-counterfeiting of exit-entry certificates with transparent windows.

Description

Technical Field

[0001] This invention relates to the field of anti-counterfeiting technology, and in particular to the application of a high-transmittance coating with self-healing properties that resists fog and frost in anti-counterfeiting, as well as anti-counterfeiting products. Background Technology

[0002] Anti-counterfeiting technologies used in entry and exit documents are divided into four levels based on the identification method. The first level is for the general public and can be identified by visual inspection alone. This level of anti-counterfeiting is visible to the naked eye and easy to identify for frontline inspectors. Based on the document production process, anti-counterfeiting technologies for entry and exit documents can be divided into material anti-counterfeiting, printing anti-counterfeiting, binding anti-counterfeiting, and issuance anti-counterfeiting. Currently, anti-counterfeiting technologies mainly target a specific production process, and there is little research on anti-counterfeiting technologies applicable to multiple production processes.

[0003] Zhang Xiaojie (Patent No.: ZL201711214650.6) disclosed a method using organosilane reagents and polymers containing carboxyl groups in the main chain or side chain as coupling agents. This method enables polymers containing hydroxyl groups in the main chain or side chain to crosslink well, forming a spatial network structure. When coated onto a substrate and dried, this forms a self-healing anti-fog and anti-frost coating. This coating exhibits good water resistance and high mechanical strength, and can withstand scrubbing and adhesive strip testing, making it suitable for anti-fog and anti-frost applications. However, there is currently no research on the application of self-healing anti-fog and anti-frost coatings in the field of anti-counterfeiting. Summary of the Invention

[0004] In view of the above-mentioned technical problems, the present invention proposes an application of a high-transmittance anti-fog and anti-frost coating with self-healing properties that overcomes or at least partially solves the above problems in anti-counterfeiting and anti-counterfeiting products.

[0005] One object of the present invention is to provide an application of a high light transmittance coating with self-healing properties that is anti-fog and anti-frost in anti-counterfeiting.

[0006] A further objective of this invention is to facilitate the visual identification of anti-counterfeiting points by frontline border inspectors.

[0007] Another further object of the present invention is to realize anti-counterfeiting technology applicable to multiple production processes of entry and exit documents.

[0008] In particular, according to one aspect of the present invention, an application of a high-transmittance anti-fog and anti-frost coating with self-healing properties in anti-counterfeiting is provided. The coating is prepared by the following steps: mixing an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain at a mass concentration of 2.2% to 50% with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid; degassing and removing precipitates from the polymer crosslinked liquid and coating it onto a solid substrate; drying to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree, wherein the crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the polymer crosslinked liquid is greater than or equal to 2%.

[0009] Optionally, the preparation steps of the high-transmittance coating with self-healing anti-fog and anti-frost properties specifically include: 1) Mix polymer powder containing hydroxyl groups in the main chain or side chain with water to prepare a polymer aqueous solution with a mass concentration of 2.2% to 50%; 2) Add the mixture of organosilane reagent and ethanol dropwise to the polymer aqueous solution obtained in step 1), stir at a water bath temperature of 0℃~100℃, adjust the pH of the solution to 1~7, continue stirring, and after the solution becomes clear, add the polymer with carboxyl groups in the main chain or side chain, stir, let it stand at room temperature to degas, and filter the liquid after standing to degas and polymer crosslinking to remove the precipitate. 3) The liquid obtained after removing the precipitate in step 2) is coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree. Among them, polymers containing hydroxyl groups in the main chain or side chain are one or more selected from polyvinyl alcohol, polyethylene glycol, and block copolymers of polyethylene glycol; polymers containing carboxyl groups in the main chain or side chain are polyacrylic acid or polymethacrylic acid.

[0010] Optionally, the organosilane reagent is selected from one or more of 3-aminopropyltriethoxysilane, chlorosilane, tetramethoxysilane, tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, γ-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0011] Optionally, anti-counterfeiting identification can be performed using the anti-fogging, anti-frost, and / or self-healing properties of a high-transmittance anti-fogging and anti-frost coating with self-healing properties. The anti-fogging and anti-frost properties of the coating do not depend on its surface structure, and the anti-counterfeiting identification is performed by visual inspection.

[0012] Optionally, the high-transmittance coating with self-healing anti-fog and anti-frost properties is applied to at least one of the following: anti-counterfeiting of materials for entry and exit documents, anti-counterfeiting of printing for entry and exit documents, anti-counterfeiting of issuance of entry and exit documents, anti-counterfeiting of binding for entry and exit documents, anti-counterfeiting of goods, and anti-counterfeiting of printed materials.

[0013] According to another aspect of the present invention, an anti-counterfeiting product is also provided, comprising: Solid substrate; and The first anti-counterfeiting coating covers at least a portion of the surface of the solid substrate; wherein The first anti-counterfeiting coating is formed by a high-transmittance coating with self-healing properties that prevents fogging and frost. The high-transmittance coating with self-healing properties that prevents fogging and frost is prepared by the following steps: an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain with a mass concentration of 2.2% to 50% is mixed with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid. The polymer crosslinked liquid is degassed and the precipitate is removed, and then coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree. The crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain of the polymer crosslinked liquid is greater than or equal to 2%.

[0014] Optionally, the first anti-counterfeiting coating is presented in the form of graphics and / or characters.

[0015] Optionally, the first anti-counterfeiting coating is a film formed by gravure printing, presenting three-dimensional graphics and / or characters.

[0016] Optionally, the first anti-counterfeiting coating comprises multiple stacked layers of high-transmittance coatings with self-healing properties, which are anti-fog and anti-frost. These multiple layers of high-transmittance coatings with self-healing properties are obtained by repeatedly coating the liquid after removing the sediment.

[0017] Optionally, the solid substrate has a transparent window; The first anti-counterfeiting coating is formed on the transparent window.

[0018] Optionally, the first anti-counterfeiting coating covers a portion of the surface of the solid substrate; Anti-counterfeiting products also include: The second anti-counterfeiting coating covers another part of the surface of the solid substrate. The second anti-counterfeiting coating is an anti-fog but non-frost-resistant coating, which is prepared by the following steps: an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain with a mass concentration of 1% to 50% is mixed with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid. The polymer crosslinked liquid is defoamed and the precipitate is removed, and then coated on the solid substrate and dried to obtain an anti-fog but non-frost-resistant coating with a network structure and controllable crosslinking degree. The crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain of the polymer in the polymer crosslinked liquid is less than 2%.

[0019] Alternatively, the solid substrate may be selected from inorganic glass, polymer sheets or films, or entry / exit documents.

[0020] This invention controls crosslinking by optimizing the ratio of the amount of hydroxyl groups in the polymer containing hydroxyl groups in the main chain or side chain to the amount of the organosilane reagent used as a crosslinking agent and the amount of the polymer containing carboxyl groups in the main chain or side chain. A crosslinked, water-resistant, long-lasting, anti-fogging, anti-frost, and high-transmittance transparent coating with self-healing properties is obtained on a solid substrate by coating method. This transparent coating is then applied directly as an anti-counterfeiting coating in the field of anti-counterfeiting, thus opening up the application of long-lasting, anti-fogging, anti-frost, and high-transmittance coatings with self-healing properties in the field of anti-counterfeiting.

[0021] Furthermore, in this invention, the anti-fogging, anti-frost, and / or self-healing properties of a high-transmittance coating with anti-fogging and anti-frost properties are used as anti-counterfeiting identification points. Moreover, the anti-fogging and anti-frost properties of the coating do not depend on the complex surface structure, thus facilitating visual identification of anti-counterfeiting by front-line border inspectors.

[0022] Furthermore, the high-transmittance coating with self-healing properties that resists fog and frost can be applied to the anti-counterfeiting processes of materials, printing, issuance, and binding of entry and exit documents, thus realizing anti-counterfeiting technology applicable to multiple production processes of entry and exit documents.

[0023] Furthermore, the anti-counterfeiting coating formed by the high light transmittance coating with self-healing anti-fog and anti-frost properties in this invention can be presented as a whole film, as graphics and / or characters, or as three-dimensional graphics and / or characters formed by gravure printing, thereby enhancing the diversity of anti-counterfeiting coatings and improving the diversity and flexibility of anti-counterfeiting identification.

[0024] Furthermore, the anti-counterfeiting coating in this invention can be formed by stacking multiple layers of self-healing, anti-fog, and anti-frost high-transmittance coatings. Since the anti-fog and anti-frost properties of the self-healing, anti-fog, and anti-frost high-transmittance coating of this invention originate from the coating's hygroscopicity and do not depend on the coating's surface structure, the overall hygroscopicity of the anti-counterfeiting coating can be enhanced by stacking multiple layers of self-healing, anti-fog, and anti-frost high-transmittance coatings, thereby enhancing the anti-fog and anti-frost properties of the anti-counterfeiting coating and improving the anti-counterfeiting identification effect.

[0025] Furthermore, in this invention, the solid substrate has a transparent window, and the anti-counterfeiting coating is formed on the transparent window. Because the coating has high light transmittance, it does not affect the performance of the transparent window itself; for example, the transparent window can be used as a decoding mirror. This anti-counterfeiting coating is particularly suitable for anti-counterfeiting purposes on entry and exit documents with transparent windows.

[0026] Furthermore, in this invention, by adjusting the concentration of the aqueous solution of the polymer containing hydroxyl groups in the main chain or side chain, the bond ratio (i.e., degree of crosslinking) of the hydroxyl groups in the aqueous solution of the polymer containing hydroxyl groups in the main chain or side chain, and the mass concentration of the uncrosslinked polymer containing hydroxyl groups in the main chain or side chain in the liquid after polymer crosslinking, anti-fogging and anti-frost coatings and anti-fogging but non-frost coatings can be obtained respectively. By respectively applying the anti-fogging and anti-frost coatings to different parts of the surface of a solid substrate, localized anti-fogging but non-frost-resistant and localized anti-fogging and anti-frost effects can be achieved, thus serving as anti-counterfeiting identification points and further broadening the diversity of anti-counterfeiting identification.

[0027] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described below.

[0028] The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments of the invention in conjunction with the accompanying drawings. Attached Figure Description

[0029] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings: Figure 1 This is a structural schematic diagram of an anti-counterfeiting product according to an embodiment of the present invention; Figure 2 This is a schematic diagram of the structure of an anti-counterfeiting product according to another embodiment of the present invention, wherein the first anti-counterfeiting coating is presented graphically. Figure 3 This is a structural schematic diagram of an anti-counterfeiting product according to another embodiment of the present invention, wherein the first anti-counterfeiting coating is presented in the form of characters; Figure 4 This is a structural schematic diagram of an anti-counterfeiting product according to another embodiment of the present invention; Figure 5 This is a structural schematic diagram of an anti-counterfeiting product according to yet another embodiment of the present invention; Figure 6 This is a schematic diagram of polycarbonate (PC) coated with a crosslinked coating according to Embodiment 1 of the present invention; Figure 7 This is a schematic diagram of a PC coated with a cross-linked coating shown in a graphic representation, according to Embodiment 1 of the present invention; Figure 8 This is a schematic diagram of a PC coated with a cross-linked coating in the form of text, according to Embodiment 1 of the present invention; Figure 9 These are anti-fogging test images of PC coated with a crosslinking coating on hot water according to Embodiment 1 of the present invention, wherein the PC coated with the crosslinking coating is on the left and the PC without the coating is on the right. Figure 10 These are anti-frost test images of PC coated with a crosslinked coating according to Embodiment 1 of the present invention, wherein the upper part of the image is PC coated with a crosslinked coating, and the lower part of the image is blank PC; Figure 11 These are the ultraviolet-visible spectra of PC coated with a crosslinking coating and blank PC in Example 1 of the present invention. Detailed Implementation

[0030] Exemplary embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey its scope to those skilled in the art. The scope of protection of the present invention should include the entirety of the claims. Unless otherwise specified, the methods involved are conventional methods. Unless otherwise specified, the reagents and materials involved are commercially available.

[0031] It should be noted that in the description of this invention, terms such as "center," "upper," "lower," "top," "bottom," "left," "right," "vertical," "horizontal," "inner," and "outer," which indicate direction or positional relationships, are based on the direction or positional relationships shown in the accompanying drawings. These are used merely for ease of description and do not indicate or imply that the device or element must have a specific orientation, or be constructed and operated in a specific orientation; therefore, they should not be construed as limitations on this invention. Furthermore, terms such as "first," "second," and "third," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0032] To address the aforementioned technical problems, embodiments of the present invention provide an application of a high-transmittance coating with self-healing properties that resists fog and frost in anti-counterfeiting applications.

[0033] A high-transmittance coating with self-healing anti-fog and anti-frost properties can be prepared by the following steps: An aqueous solution of a polymer containing hydroxyl groups in its main chain or side chains (mass concentration 2.2%~50%) is mixed with an organosilane reagent and a polymer containing carboxyl groups in its main chain or side chains to obtain a cross-linked polymer liquid. After degassing and removing precipitates, the cross-linked polymer liquid is coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable cross-linking degree. The cross-linking degree of the polymer containing hydroxyl groups in its main chain or side chains is 5%~80%, and the mass concentration of uncross-linked polymers containing hydroxyl groups in the cross-linked polymer liquid is greater than or equal to 2%.

[0034] The degree of crosslinking of a polymer (i.e., the hydroxyl bonding rate) is determined by the ratio of the amount of hydroxyl groups participating in the crosslinking reaction in the polymer containing hydroxyl groups in the main chain or side chain to the amount of hydroxyl groups in the polymer containing hydroxyl groups in the main chain or side chain before the crosslinking reaction. The degree of crosslinking of the prepared anti-fogging and anti-frost high-transmittance coating can be controlled by adjusting the ratio of the amount of hydroxyl groups in the polymer containing hydroxyl groups in the main chain or side chain to the amount of the organosilane reagent used as a crosslinking agent and the amount of the polymer containing carboxyl groups in the main chain or side chain.

[0035] In some embodiments, the ratio of the amount of hydroxyl groups in a polymer containing hydroxyl groups in the main chain or side chain to the amount of organosilane reagent is 5:1 to 1:0.

[0036] In some embodiments, the ratio of the amount of hydroxyl groups in the polymer containing hydroxyl groups in the main chain or side chain to the amount of carboxyl groups in the polymer containing carboxyl groups in the main chain or side chain is 1:1 to 1:0.

[0037] This invention utilizes a crosslinking method involving polymers containing hydroxyl groups in their main chain or side chains with organosilane reagents and polymers containing carboxyl groups in their main chain or side chains to prepare a water-resistant, long-lasting, anti-fogging, and anti-frost coating with high light transmittance. The hydroxyl bonding rate (a quantitative indicator of the degree of crosslinking) of the polymers containing hydroxyl groups in their main chain or side chains is a crucial factor affecting the anti-fogging, anti-frost, and water resistance properties of the coating obtained from polymers containing hydroxyl groups in their main chain or side chains. This invention focuses on the influence of the hydroxyl bonding rate of polymers containing hydroxyl groups in the main chain or side chain on the anti-fogging performance and water resistance of coatings obtained from polymers containing hydroxyl groups in the main chain or side chain. Crosslinking is controlled by optimizing the ratio of the amount of hydroxyl groups in the polymer containing hydroxyl groups in the main chain or side chain to the amount of organosilane reagent used as a crosslinking agent and the amount of the polymer containing carboxyl groups in the main chain or side chain. A crosslinked, self-healing, water-resistant, long-lasting, anti-fogging, anti-frost, and high-transmittance transparent coating with high light transmittance is obtained on a solid substrate by coating method. This transparent coating is then applied directly as an anti-counterfeiting coating in the field of anti-counterfeiting, thus opening up the application of long-lasting, anti-fogging, anti-frost, and self-healing high-transmittance coatings in the field of anti-counterfeiting.

[0038] In some embodiments, the preparation steps of the self-healing, anti-fogging, and anti-frost high-transmittance coating specifically include: 1) Mix the polymer powder containing hydroxyl groups in the main chain or side chain with water to prepare a polymer aqueous solution with a mass concentration of 2.2% to 50%; 2) Add the mixture of the organosilane reagent and ethanol dropwise to the polymer aqueous solution obtained in step 1), stir at a water bath temperature of 0℃~100℃, adjust the pH of the solution to 1~7, continue stirring, and after the solution becomes clear, add the polymer containing carboxyl groups in the main chain or side chain, stir, let it stand at room temperature to degas, and filter the liquid after standing to degas and polymer crosslinking to remove the precipitate. 3) The liquid obtained after removing the precipitate in step 2) is coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree.

[0039] Specifically, step 1) can be carried out under water bath heating and stirring conditions. The heating temperature is, for example, 80℃~100℃, preferably 85℃~100℃. The mass fraction of the prepared polymer aqueous solution is 2.2%~50%, for example 2.5%, 3%, 4%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%. Preferably, the mass fraction of the prepared polymer aqueous solution is 5%~20%.

[0040] In step 2), the mass ratio of the organosilane reagent to ethanol in the mixture is 1:10 to 1:0. The water bath temperature is 0℃ to 100℃, preferably 30℃ to 90℃. The stirring time is 0.2 to 72 hours, preferably 0.3 to 7 hours. The pH can be adjusted by adding an inorganic acid. The inorganic acid can be selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The standing degassing time is 0.2 to 72 hours, preferably 0.3 to 7 hours.

[0041] Step 3) can be applied using any of the following methods: dip coating, spray coating, spin coating, scraping coating, roller coating, manual application, printing, or printing. Drying can be done by air drying or oven drying. When drying in an oven, the drying temperature range is 20°C to 150°C.

[0042] In some embodiments, the polymer containing hydroxyl groups in the main chain or side chain is one or more selected from polyvinyl alcohol, polyethylene glycol, and polyethylene glycol block copolymers.

[0043] In some embodiments, the polymer containing carboxyl groups in the main chain or side chain is polyacrylic acid or polymethacrylic acid.

[0044] In some embodiments, the organosilane reagent is selected from one or more of 3-aminopropyltriethoxysilane, chlorosilane, tetramethoxysilane, tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, γ-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0045] In some embodiments, the solid substrate is selected from inorganic glass, polymer sheets or films, or entry / exit documents, etc.

[0046] Inorganic glass includes, for example, K7105 glass, 5 mm thick process glass, and glass slides.

[0047] Polymer sheets or films can be, for example, polycarbonate (PC), polymethyl methacrylate (PMMA), automotive sun protection film, resin lenses, polyethylene terephthalate (PET), etc.

[0048] Entry and exit documents may include, for example, entry and exit documents with transparent windows (such as passports, seamen's books) information pages and visa pages, card-type entry and exit documents, etc.

[0049] In some embodiments, in the application of the self-healing, anti-fog, and anti-frost high-transmittance coating of the present invention in anti-counterfeiting, anti-counterfeiting identification is performed by the anti-fog phenomenon, anti-frost phenomenon, and / or self-healing phenomenon of the self-healing, anti-fog, and anti-frost high-transmittance coating. Furthermore, the anti-fog and anti-frost performance of the self-healing, anti-fog, and anti-frost high-transmittance coating does not depend on its surface structure (i.e., it does not require the formation of a complex surface structure on the coating surface), and anti-counterfeiting identification can be performed visually.

[0050] In this embodiment, the anti-fogging, anti-frost, and / or self-healing properties of a high-transmittance coating with anti-fogging and anti-frost properties are used as anti-counterfeiting identification points. Moreover, the anti-fogging and anti-frost properties of the coating do not depend on the complex surface structure, thus facilitating visual identification of anti-counterfeiting by front-line border inspectors.

[0051] In some embodiments, the high-transmittance coating with self-healing anti-fog and anti-frost properties is applied to at least one of the following: anti-counterfeiting of materials for entry and exit documents, anti-counterfeiting of printing for entry and exit documents, anti-counterfeiting of issuance of entry and exit documents, anti-counterfeiting of binding for entry and exit documents, anti-counterfeiting of goods, and anti-counterfeiting of printed materials.

[0052] Specifically, for example, the high-transmittance coating with self-healing properties that resists fog and frost can be applied to the surface of the printing material of entry and exit documents as an anti-counterfeiting coating, printed onto entry and exit documents as a printing material to form an anti-counterfeiting coating, used as an anti-counterfeiting coating when adding issuance object information to entry and exit documents to achieve issuance anti-counterfeiting, applied to the binding transparent hinge of entry and exit documents to achieve binding anti-counterfeiting, and can also be applied to the surface of goods or printed materials to achieve anti-counterfeiting.

[0053] Therefore, the high-transmittance coating with self-healing properties that resists fog and frost in this invention can be applied to the anti-counterfeiting processes of materials, printing, issuance, and binding of entry and exit documents. In other words, it realizes anti-counterfeiting technology applicable to multiple production processes of entry and exit documents.

[0054] In some embodiments, the high-transmittance coating with self-healing anti-fog and anti-frost properties can be a single sheet of film, a film displaying graphics, a film displaying text, or a film combining graphics and text. The graphic coating can display graphic shapes and content during anti-fog and anti-frost testing.

[0055] In some embodiments, when coating is applied to form a coating, the coating may completely cover the solid substrate or partially cover the solid substrate.

[0056] In some embodiments, high-transmittance coatings with self-healing properties, exhibiting varying numbers and thicknesses, can be obtained through multiple coating processes. Since the anti-fog and anti-frost properties of the high-transmittance coating with self-healing properties of the present invention originate from the coating's hygroscopicity and do not depend on the coating's surface structure, the overall hygroscopicity of the coating can be enhanced by forming multiple layers of high-transmittance coatings with self-healing properties or by increasing the thickness of the high-transmittance coating with self-healing properties, thereby enhancing the coating's anti-fog and anti-frost properties and improving anti-counterfeiting identification effects.

[0057] In some embodiments, a film with a three-dimensional graphic structure is obtained by gravure printing, which can better highlight the shape and content of the graphic during anti-fog and anti-frost tests.

[0058] In some embodiments, a membrane that provides partial anti-fogging but not anti-frost protection, or partial anti-fogging and anti-frost protection, can be obtained by adjusting the concentration of the aqueous solution of the polymer containing hydroxyl groups in the main chain or side chain, the bond ratio of hydroxyl groups in the aqueous solution of the polymer containing hydroxyl groups in the main chain or side chain, and the mass concentration of the uncrosslinked polymer containing hydroxyl groups in the main chain or side chain in the liquid after polymer crosslinking.

[0059] Since the amount of hydroxyl groups remaining after bonding determines the anti-frost properties of the resulting coating, different anti-frost properties can be achieved by adjusting the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chains of the crosslinked polymer liquid. Specifically, adjusting the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chains of the crosslinked polymer liquid to greater than or equal to 2% yields an anti-fogging and anti-frost coating; adjusting the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chains of the crosslinked polymer liquid to less than 2% yields an anti-fogging but not anti-frost coating. Combining these two types of coatings can produce films that are locally anti-fogging but not anti-frost, or locally anti-fogging and anti-frost.

[0060] Based on the same technical concept, embodiments of the present invention also provide an anti-counterfeiting product 100.

[0061] Figure 1 This is a structural schematic diagram of an anti-counterfeiting product 100 according to an embodiment of the present invention. Figure 1 As shown, the anti-counterfeiting product 100 includes: a solid substrate 110; and a first anti-counterfeiting coating 120, which covers at least a portion of the surface of the solid substrate 110. The first anti-counterfeiting coating 120 may completely cover the surface of the solid substrate 110, or it may only cover a portion of the surface of the solid substrate 110 (i.e., partially cover the surface of the solid substrate 110).

[0062] The first anti-counterfeiting coating 120 is formed from the aforementioned high-transmittance coating with self-healing properties that is also anti-fog and anti-frost. The preparation steps of the high-transmittance coating with self-healing properties that is also anti-fog and anti-frost are as described above and will not be repeated here.

[0063] Figure 2 This is a schematic diagram of the structure of an anti-counterfeiting product 100 according to another embodiment of the present invention, wherein the first anti-counterfeiting coating 120 is presented graphically. Figure 3 This is a structural schematic diagram of an anti-counterfeiting product 100 according to another embodiment of the present invention, wherein the first anti-counterfeiting coating 120 is presented in the form of characters.

[0064] like Figure 2 As shown, in some embodiments, the first anti-counterfeiting coating 120 is presented graphically.

[0065] like Figure 3 As shown, in some embodiments, the first anti-counterfeiting coating 120 is presented as characters. Characters may include, for example, text, letters, symbols, numbers, etc.

[0066] In some other embodiments, the first anti-counterfeiting coating 120 is presented as a combination of graphics and characters.

[0067] It should be noted that, Figure 2 and Figure 3 The graphics and characters shown are merely illustrative and do not limit the invention.

[0068] In some other embodiments, the first anti-counterfeiting coating 120 may be a film formed by gravure printing, presenting three-dimensional graphics and / or characters.

[0069] In embodiments of the present invention, the anti-counterfeiting coating formed by the high light transmittance coating with self-healing anti-fog and anti-frost properties can be presented as a whole film, or as graphics and / or characters, or as three-dimensional graphics and / or characters formed by gravure printing, thereby enhancing the diversity of the anti-counterfeiting coating and improving the diversity and flexibility of anti-counterfeiting identification.

[0070] In some embodiments, the first anti-counterfeiting coating 120 may include stacked multilayer anti-fog and anti-frost high-transmittance coatings with self-healing properties. This multilayer anti-fog and anti-frost high-transmittance coating is obtained by repeatedly coating a cross-linked liquid after removing deposits.

[0071] In this embodiment of the invention, the anti-counterfeiting coating can be formed by stacking multiple layers of self-healing, anti-fog, and anti-frost high-transmittance coatings. Since the anti-fog and anti-frost properties of the self-healing, anti-fog, and anti-frost high-transmittance coating of this invention originate from the coating's hygroscopicity and do not depend on the coating's surface structure, the overall hygroscopicity of the anti-counterfeiting coating can be enhanced by stacking multiple layers of self-healing, anti-fog, and anti-frost high-transmittance coatings, thereby enhancing the anti-fog and anti-frost properties of the anti-counterfeiting coating and improving the anti-counterfeiting identification effect.

[0072] Figure 4 This is a structural schematic diagram of an anti-counterfeiting product 100 according to another embodiment of the present invention. Figure 4 As shown, in some embodiments, the solid substrate 110 may have a transparent window 111, on which a first anti-counterfeiting coating 120 is formed. It should be noted that... Figure 4 The shape of the transparent window 111 shown is merely exemplary and does not limit the invention. In practical applications, the transparent window 111 can be any desired shape. Furthermore, Figure 4 The relative size relationship between the first anti-counterfeiting coating 120 and the transparent window 111 shown is only illustrative. The first anti-counterfeiting coating 120 may cover only a part of the transparent window 111 or it may cover the entire transparent window 111.

[0073] In this embodiment, the solid substrate 110 has a transparent window 111, and an anti-counterfeiting coating is formed on the transparent window 111. Because the coating has high light transmittance, it does not affect the performance of the transparent window itself; for example, the transparent window can be used as a decoding mirror. This anti-counterfeiting coating is particularly suitable for anti-counterfeiting purposes on entry and exit documents with a transparent window 111.

[0074] Figure 5 This is a structural schematic diagram of an anti-counterfeiting product 100 according to yet another embodiment of the present invention. Figure 5 As shown, in some embodiments, the first anti-counterfeiting coating 120 covers a portion of the surface of the solid substrate 110. The anti-counterfeiting product 100 also includes a second anti-counterfeiting coating 130. The second anti-counterfeiting coating 130 covers another portion of the surface of the solid substrate 110. It should be noted that... Figure 5 The relative positions of the first anti-counterfeiting coating 120 and the second anti-counterfeiting coating 130 shown are merely illustrative and do not limit the invention. The first anti-counterfeiting coating 120 and the second anti-counterfeiting coating 130 may be adjacent to each other or separated from each other. Furthermore, the combination of the first anti-counterfeiting coating 120 and the second anti-counterfeiting coating 130 may completely cover the surface of the solid substrate 110 or only cover a portion of the surface of the solid substrate 110.

[0075] The second anti-counterfeiting coating 130 is an anti-fog but non-frost-resistant coating, prepared by the following steps: an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain with a mass concentration of 1% to 50% is mixed with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid; the polymer crosslinked liquid is defoamed and the precipitate is removed, and then coated onto a solid substrate 110 and dried to obtain an anti-fog but non-frost-resistant coating with a network structure and controllable crosslinking degree, wherein the crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain of the polymer in the polymer crosslinked liquid is less than 2%.

[0076] In other words, the preparation steps of the anti-fog but non-frost-resistant coating are basically the same as those of the high-transmittance anti-fog and anti-frost coating with self-healing properties. The difference is that by adjusting the mass concentration of the aqueous solution of the polymer containing hydroxyl groups in the main chain or side chain and the degree of crosslinking of the polymer containing hydroxyl groups in the main chain or side chain, the mass concentration of the uncrosslinked polymer containing hydroxyl groups in the main chain or side chain in the liquid after polymer crosslinking is less than 2%.

[0077] In this embodiment of the invention, by adjusting the concentration of the aqueous solution of polymers containing hydroxyl groups in the main chain or side chain, the bond ratio (i.e., degree of crosslinking) of hydroxyl groups in the aqueous solution of polymers containing hydroxyl groups in the main chain or side chain, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain in the crosslinked liquid, anti-fogging and anti-frost coatings and anti-fogging but non-frost coatings can be obtained respectively. By respectively applying the anti-fogging and anti-frost coatings to different parts of the surface of the solid substrate 110, local anti-fogging but non-frost-resistant effects and local anti-fogging and anti-frost effects can be achieved, thus serving as anti-counterfeiting identification points and further broadening the diversity of anti-counterfeiting identification.

[0078] In some embodiments, when the solid substrate 110 has a transparent window 111, the first anti-counterfeiting coating 120 and the second anti-counterfeiting coating 130 may both be formed on the transparent window 111.

[0079] The technical solution of the present invention will be further described below through some more specific embodiments.

[0080] Example 1 Preparation and performance testing of a high-transmittance anti-fog and anti-frost coating with self-healing properties, characterized by a polyvinyl alcohol (PVA) crosslinking degree (hydroxyl bonding rate) of 5% to less than 50%.

[0081] 1) In a container, PVA powder is mixed with water and heated in a water bath at 85°C with stirring to prepare a 10% PVA aqueous solution by mass. 2) Add dropwise a mixture of 0.30 ml to 3.14 ml tetraethyl orthosilicate (TEOS) and ethanol (mass ratio 1:3) to 50 g of the 10% PVA aqueous solution obtained in step 1). Stir for 0.2 to 72 hours at a water bath temperature of 0℃ to 100℃. Add nitric acid to adjust the pH of the solution to 1 to 7, and continue stirring for 0.2 to 72 hours. After the solution becomes clear, add 0.05 g of 53% polyacrylic acid (PAA) aqueous solution, stir for 0.2 to 72 hours, and allow to stand at room temperature for 0.2 to 72 hours to remove bubbles. Filter the liquid after standing and degassing and PVA crosslinking (crosslinking degree greater than or equal to 5% to less than 50%) to remove precipitates. 3) The liquid obtained after filtration to remove the precipitate in step 2) is coated onto inorganic glass (such as K7105 glass, 5 mm thick process glass, glass slides, etc.), polymer sheets or films (such as polycarbonate (PC), polymethyl methacrylate (PMMA), automotive sun protection film, resin lenses, polyethylene terephthalate (PET)), information pages and visa pages of entry and exit documents (passports, seaman's books) with transparent windows, card-type entry and exit documents, etc., using methods such as lifting, spraying, spin coating, scraping, rolling, manual application, printing or printing. It is then air-dried or dried in an oven at 20℃~150℃ to obtain a water-resistant, long-lasting anti-fog and anti-frost transparent coating with a network structure and controllable cross-linking degree (hereinafter referred to as cross-linking coating).

[0082] The ratio of the amount of hydroxyl groups participating in the crosslinking reaction of PVA in the polymer crosslinking to the amount of hydroxyl groups in PVA before the polymer crosslinking reaction determines the degree of crosslinking (hydroxyl bonding rate) of PVA in the resulting water-resistant, long-lasting, anti-fog, and anti-frost transparent coating with a network structure and controllable crosslinking degree, which is greater than or equal to 5% and less than 50%. Figure 6 This is a schematic diagram of the PC coated with a crosslinked coating in Example 1. Figure 7 This is a schematic diagram of the PC coated with the cross-linked coating shown in the graphic representation in Example 1. Figure 8 This is a schematic diagram of a PC coated with a cross-linked coating in the form of text, as shown in Example 1.

[0083] The anti-fogging and anti-frost properties of the obtained transparent coating: such as anti-fogging on breath and anti-fogging on saturated water vapor at 50°C, the results are as follows. Figure 9 As shown; after placing it in a -20℃ refrigerator for 24 hours to prevent frost, it was immediately photographed after being removed, and the results are as follows. Figure 10 As shown. In the water resistance test, after immersing the sample in water at 50°C for 100 minutes, the transparent coating did not peel off, and after drying, it still exhibited excellent anti-fogging and anti-frost properties. Figure 11As shown, the transparent coating has high light transmittance. The light transmittance of the aforementioned transparent PC solid substrate is slightly increased after coating with the transparent coating compared to the blank substrate. Hardness test: When the transparent coating is scratched with a pencil of a certain hardness, and then exposed to hot water or atomized with an atomizer, the scratches become lighter or even disappear, indicating that the transparent coating has scratch self-healing properties. This self-healing property mainly comes from the polymer's fluidity and the reformation of hydrogen bonds after breakage at the interface. Cleaning resistance: After 50 washes, the transparent coating shows no change, maintaining good anti-fogging and anti-frost properties. Scrub resistance test: After 50 scrubs, the transparent coating shows no change, maintaining good anti-fogging and anti-frost properties, and the light transmittance does not change significantly. Adhesive strip test: After 100 adhesive strip tests, the transparent coating shows no change, maintaining good anti-fogging and anti-frost properties.

[0084] Example 2 Preparation and performance testing of a high-transmittance coating with self-healing properties, anti-fogging and anti-frost, having a PVA crosslinking degree (hydroxyl bonding rate) of ≥50% to ≤80%.

[0085] 1) In a container, PVA powder is mixed with water and heated in a water bath at 85°C with stirring to prepare a 10% PVA aqueous solution by mass. 2) Add 3.15 ml to 5.05 ml of a mixture of tetraethyl orthosilicate (TEOS) and ethanol (mass ratio 1:3) dropwise to 50 g of a 10% PVA aqueous solution obtained in step 1). Stir for 0.2 to 72 hours at a water bath temperature of 0°C to 100°C. Add nitric acid to adjust the pH of the solution to 1 to 7, and continue stirring for 0.2 to 72 hours. After the solution becomes clear, add 0.05 g of a 53% polyacrylic acid (PAA) aqueous solution, stir for 0.2 to 72 hours, and allow to stand at room temperature for 0.2 to 72 hours to remove bubbles. Filter the liquid after standing and degassing and PVA crosslinking (crosslinking degree greater than or equal to 50% to less than or equal to 80%) to remove precipitates. 3) The liquid obtained after filtration to remove the precipitate in step 2) is coated onto inorganic glass (such as K7105 glass, 5 mm thick process glass, glass slides, etc.), polymer sheets or films (such as polycarbonate (PC), polymethyl methacrylate (PMMA), automotive sun protection film, resin lenses, polyethylene terephthalate (PET)), information pages and visa pages of entry and exit documents (passports, seaman's books) with transparent windows, card-type entry and exit documents, etc., using methods such as lifting, spraying, spin coating, scraping, rolling, manual application, printing, etc., and then air-dried or dried in an oven at 20℃~150℃ to obtain a water-resistant, long-lasting, anti-fog and anti-frost transparent coating with a network structure and controllable cross-linking degree.

[0086] The ratio of the amount of hydroxyl groups participating in the crosslinking reaction of PVA in the polymer crosslinking to the amount of hydroxyl groups in PVA before the polymer crosslinking reaction determines the degree of crosslinking (hydroxyl bonding rate) of PVA in the resulting transparent coating with controllable crosslinking degree of network structure, which is greater than or equal to 50% and less than or equal to 80%.

[0087] The obtained transparent coating exhibits the following anti-fogging and anti-frost properties: anti-fogging upon exhalation, anti-fogging on saturated water vapor at 50℃, and anti-frost after 24 hours in a -20℃ refrigerator; in the water resistance test, after immersing the sample in 50℃ water for 100 minutes, the transparent coating did not peel off and maintained excellent anti-fogging and anti-frost properties after drying; the transparent coating has high light transmittance, with the light transmittance of the aforementioned transparent solid substrate slightly increased compared to the blank substrate after coating; hardness test: after scratching the transparent coating with a pencil of a certain hardness, it remained effective under heat... When fumigated with water or atomized with an atomizer, the scratches become lighter or even disappear, indicating that the transparent coating has self-healing properties. This self-healing property mainly comes from the polymer's fluidity and the reformation of hydrogen bonds after breakage at the interface. Washing resistance: After 50 washes, the transparent coating shows no change, maintaining good anti-fog and anti-frost performance. Scrub resistance test: After 50 scrubs, the transparent coating shows no change, maintaining good anti-fog and anti-frost performance, and the light transmittance does not change significantly. Adhesive strip test: After 100 adhesive strip tests, the transparent coating shows no change, maintaining good anti-fog and anti-frost performance.

[0088] Example 3 Preparation and performance testing of coatings that have anti-fog properties but are not frost resistant.

[0089] 1) In a container, PVA powder is mixed with water and heated in a water bath at 85°C with stirring to prepare a 5% PVA aqueous solution by mass. 2) Add 1.88 ml of a mixture of tetraethyl orthosilicate (TEOS) and ethanol (mass ratio 1:7) dropwise to 50 g of a 5% PVA aqueous solution obtained in step 1). Stir for 0.2 to 72 hours at a water bath temperature of 0℃ to 100℃. Add nitric acid to adjust the pH of the solution to 1 to 7 and continue stirring for 0.2 to 72 hours. After the solution becomes clear, add 0.05 g of a 53% polyacrylic acid (PAA) aqueous solution and stir for 0.2 to 72 hours. Let the solution stand at room temperature for 0.2 to 72 hours to remove bubbles. Filter the liquid after standing for degassing and PVA crosslinking (crosslinking degree of 60%) to remove precipitates. 3) The liquid obtained after filtration to remove the precipitate in step 2) is coated onto inorganic glass (such as K7105 glass, 5 mm thick process glass, glass slides, etc.), polymer sheets or films (such as polycarbonate (PC), polymethyl methacrylate (PMMA), automotive sun protection film, resin lenses, polyethylene terephthalate (PET)), information pages and visa pages of entry and exit documents (passports, seaman's books) with transparent windows, card-type entry and exit documents, etc., using methods such as lifting, spraying, spin coating, scraping, rolling, manual application, and printing. It is then air-dried or dried in an oven at 20℃~150℃ to obtain a transparent coating with a network structure, controllable cross-linking degree, water resistance, long-lasting anti-fog, and non-frost-resistant properties.

[0090] The ratio of the amount of hydroxyl groups participating in the crosslinking reaction of PVA during polymer crosslinking to the amount of hydroxyl groups in PVA before the polymer crosslinking reaction determines the degree of crosslinking (hydroxyl bond rate) of PVA in the resulting water-resistant, long-lasting, anti-fogging but not anti-frost transparent coating with a network structure and controllable crosslinking degree, which is 60%. The mass fraction and amount of PVA aqueous solution used for crosslinking, the amounts of tetraethyl orthosilicate and ethanol, the mass fraction and amount of polyacrylic acid aqueous solution, and the degree of crosslinking of PVA determine that the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chains in the liquid after polymer crosslinking is less than 2%.

[0091] The obtained transparent coating exhibits the following anti-fogging and anti-frost properties: It prevents fogging upon exhalation, resists fogging on saturated water vapor at 50°C, and shows no anti-frost properties after being placed in a -20°C refrigerator for 24 hours. In the water resistance test, after immersing the sample in 50°C water for 100 minutes, the transparent coating did not peel off and maintained excellent anti-fogging performance after drying. The transparent coating has high light transmittance; the light transmittance of the aforementioned transparent solid substrate is slightly increased compared to the blank substrate after coating. Hardness test: When scratched with a pencil of a certain hardness, the transparent coating shows no signs of damage. When exposed to hot water or atomized with a misting device, scratches become lighter or even disappear, indicating that the transparent coating has self-healing properties. This self-healing property mainly comes from the polymer's fluidity and the reformation of hydrogen bonds after breakage at the interface. Cleaning resistance: After 50 washes, the transparent coating shows no change, maintaining good anti-fogging performance. Scrub resistance test: After 50 scrubs, the transparent coating shows no change, maintaining good anti-fogging performance, and the light transmittance does not change significantly. Adhesive strip test: After 100 adhesive strip tests, the transparent coating shows no change, maintaining good anti-fogging performance.

[0092] Example 4 Example 4 is basically the same as Example 1, except that tetraethyl orthosilicate is replaced with 3-aminopropyltriethoxysilane, chlorosilane, tetramethoxysilane, propyl orthosilicate or isopropyl orthosilicate, and 3-glycidyl etheroxypropyltrimethoxysilane is replaced with one or more selected from γ-aminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane. All of these methods yield the same results as Example 1.

[0093] Example 5 Example 5 is basically the same as Example 1, except that nitric acid is replaced with hydrochloric acid, sulfuric acid or phosphoric acid, and the same results as in Example 1 are obtained.

[0094] Example 6 Example 6 is basically the same as Example 1, except that nitric acid is replaced with hydrochloric acid, sulfuric acid or phosphoric acid to adjust the pH of the solution to 1-7, and the same results as in Example 1 are obtained.

[0095] Example 7 Example 7 is basically the same as Example 1, except that polyvinyl alcohol is replaced with other polymers containing hydroxyl groups in the main chain or side chain, such as polyethylene glycol, polyethylene glycol block copolymers or one or more of them. The same results as in Example 1 can be obtained.

[0096] Example 8 Example 8 is basically the same as Example 1, except that polyacrylic acid is replaced with other polymers containing hydroxyl groups in the main chain or side chain, such as polymethacrylic acid. The same results as in Example 1 are obtained.

[0097] The beneficial effects of this invention are as follows: This invention pioneers the application of a high-transmittance coating with long-lasting anti-fog and anti-frost properties and self-healing properties in the field of anti-counterfeiting.

[0098] 1. This invention optimizes the ratio of the amount of hydroxyl groups in polymers containing hydroxyl groups in the main chain or side chains to the amount of the crosslinking agent, and obtains a crosslinked, self-healing, water-resistant, long-lasting, anti-fog, anti-frost, and high-transmittance transparent coating on a solid substrate by coating method.

[0099] 2. The anti-counterfeiting features of this coating are anti-fog, anti-frost, and self-healing. Its excellent characteristics include high light transmittance, anti-fog and anti-frost performance that does not depend on complex surface structures, and visual identification by the public.

[0100] 3. This coating can be applied in the anti-counterfeiting processes of entry and exit document materials, printing anti-counterfeiting, issuance anti-counterfeiting, and binding anti-counterfeiting production.

[0101] 4. This coating can be a single sheet of film, a film displaying graphics, a film displaying text, or a film combining graphics and text. Combining anti-fog and anti-frost performance with graphics and text serves as an anti-counterfeiting identification point. The coating with graphics and text can display the shape and content of the graphics and text during anti-fog and anti-frost tests.

[0102] 5. This coating can cover the entire substrate or only a portion of it.

[0103] 6. Films with different numbers of layers and thicknesses can be obtained through multiple coating processes.

[0104] 7. A film with a three-dimensional graphic structure can be obtained through gravure printing, and the shape and content of the graphic can be more prominently displayed during anti-fog and anti-frost tests.

[0105] 8. By adjusting the concentration of the aqueous solution of polymers containing hydroxyl groups in the main chain or side chain, the bond ratio of hydroxyl groups in the aqueous solution of polymers containing hydroxyl groups in the main chain or side chain, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain in the crosslinked polymer liquid, a film that is locally anti-fogging but not anti-frost, or locally anti-fogging and anti-frost, can be obtained as an anti-counterfeiting identification point.

[0106] 9. The anti-counterfeiting applications and products of the present invention are widely applicable in the field of anti-counterfeiting, such as inorganic glass (e.g., K7105 glass, 5 mm thick process glass, glass slides, etc.), polymer sheets or films (e.g., PC, PMMA, automotive sun protection film, resin lenses, PET), information pages and visa pages of entry and exit documents (passports, seaman's books) with transparent windows, card-type entry and exit documents, and other materials.

[0107] Numerous specific details are set forth in the specification provided herein. However, it will be understood that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures, and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0108] Therefore, those skilled in the art should recognize that although numerous exemplary embodiments of the present invention have been shown and described in detail herein, many other variations or modifications conforming to the principles of the present invention can be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Thus, the scope of the present invention should be understood and construed as covering all such other variations or modifications.

Claims

1. The application of a high-transmittance coating with self-healing properties, anti-fog and anti-frost properties, in anti-counterfeiting applications, characterized in that... The coating is prepared by the following steps: A 2.2%–50% (w / w) aqueous solution of a polymer containing hydroxyl groups in its main chain or side chains is mixed with an organosilane reagent and a polymer containing carboxyl groups in its main chain or side chains to obtain a cross-linked polymer liquid. The cross-linked polymer liquid is degassed and precipitated, then coated onto a solid substrate and dried to obtain an anti-fogging and anti-frost coating with a network structure and controllable cross-linking degree. The cross-linking degree of the polymer containing hydroxyl groups in its main chain or side chains is 5%–80%, and the mass concentration of uncross-linked polymers containing hydroxyl groups in the cross-linked polymer liquid is greater than or equal to 2%.

2. The application of the high-transmittance coating with self-healing properties, anti-fog and anti-frost properties, as described in claim 1, in anti-counterfeiting, characterized in that... The preparation steps of the coating specifically include: 1) Mix the polymer powder containing hydroxyl groups in the main chain or side chain with water to prepare a polymer aqueous solution with a mass concentration of 2.2% to 50%; 2) Add the mixture of the organosilane reagent and ethanol dropwise to the polymer aqueous solution obtained in step 1), stir at a water bath temperature of 0℃~100℃, adjust the pH of the solution to 1~7, continue stirring, and after the solution becomes clear, add the polymer containing carboxyl groups in the main chain or side chain, stir, let it stand at room temperature to degas, and filter the liquid after standing to degas and polymer crosslinking to remove the precipitate. 3) The liquid obtained after removing the precipitate in step 2) is coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree. Wherein, the polymer containing hydroxyl groups in the main chain or side chain is one or more selected from polyvinyl alcohol, polyethylene glycol, and block copolymers of polyethylene glycol; the polymer containing carboxyl groups in the main chain or side chain is polyacrylic acid or polymethacrylic acid.

3. The application of the high-transmittance coating with self-healing properties, anti-fog and anti-frost properties, as described in claim 2, in anti-counterfeiting, characterized in that... The organosilane reagent is selected from one or more of 3-aminopropyltriethoxysilane, chlorosilane, tetramethoxysilane, tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, γ-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

4. The application of the high-transmittance coating with self-healing properties for anti-fogging and anti-frost according to any one of claims 1-3 in anti-counterfeiting, characterized in that, Anti-counterfeiting identification is achieved through the anti-fogging, anti-frost, and / or self-healing properties of the coating. The anti-fogging and anti-frost performance of the coating does not depend on its surface structure, and anti-counterfeiting identification is performed by visual inspection.

5. The application of the high-transmittance coating with self-healing properties for anti-fogging and anti-frost according to any one of claims 1-3 in anti-counterfeiting, characterized in that, The coating is applied to at least one of the following: anti-counterfeiting of materials for entry and exit documents, anti-counterfeiting of printing for entry and exit documents, anti-counterfeiting of issuance of entry and exit documents, anti-counterfeiting of binding for entry and exit documents, anti-counterfeiting of goods, and anti-counterfeiting of printed matter.

6. An anti-counterfeiting product, comprising: Solid substrate; as well as A first anti-counterfeiting coating covers at least a portion of the surface of the solid substrate; characterized in that... The first anti-counterfeiting coating is formed by a high-transmittance coating with self-healing properties that prevents fogging and frost. The high-transmittance coating with self-healing properties is prepared by the following steps: an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain with a mass concentration of 2.2% to 50% is mixed with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid. The polymer crosslinked liquid is defoamed and the precipitate is removed, and then coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree. The crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the polymer crosslinked liquid is greater than or equal to 2%.

7. The anti-counterfeiting product according to claim 6, characterized in that, The preparation steps of the high light transmittance coating with self-healing anti-fog and anti-frost properties specifically include: 1) Mix the polymer powder containing hydroxyl groups in the main chain or side chain with water to prepare a polymer aqueous solution with a mass concentration of 2.2% to 50%; 2) Add the mixture of the organosilane reagent and ethanol dropwise to the polymer aqueous solution obtained in step 1), stir at a water bath temperature of 0℃~100℃, adjust the pH of the solution to 1~7, continue stirring, and after the solution becomes clear, add the polymer containing carboxyl groups in the main chain or side chain, stir, let it stand at room temperature to degas, and filter the liquid after standing to degas and polymer crosslinking to remove the precipitate. 3) The liquid obtained after removing the precipitate in step 2) is coated onto a solid substrate and dried to obtain an anti-fog and anti-frost coating with a network structure and controllable crosslinking degree. Wherein, the polymer containing hydroxyl groups in the main chain or side chain is one or more selected from polyvinyl alcohol, polyethylene glycol, and polyethylene glycol block copolymers; The polymer containing carboxyl groups in its main chain or side chain is polyacrylic acid or polymethacrylic acid; The organosilane reagent is selected from one or more of 3-aminopropyltriethoxysilane, chlorosilane, tetramethoxysilane, tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, γ-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

8. The anti-counterfeiting product according to claim 6, characterized in that, The first anti-counterfeiting coating is presented in the form of graphics and / or characters.

9. The anti-counterfeiting product according to claim 6, characterized in that, The first anti-counterfeiting coating is a film formed by gravure printing, which presents three-dimensional graphics and / or characters.

10. The anti-counterfeiting product according to claim 6, characterized in that, The first anti-counterfeiting coating comprises multiple stacked layers of high-transmittance coatings with self-healing properties, which are anti-fog and anti-frost. These multiple layers of high-transmittance coatings with self-healing properties are obtained by repeatedly coating the liquid obtained after removing the sediment.

11. The anti-counterfeiting product according to any one of claims 6-10, characterized in that, The solid substrate has a transparent viewing window; The first anti-counterfeiting coating is formed on the transparent window.

12. The anti-counterfeiting product according to claim 6, characterized in that, The first anti-counterfeiting coating covers a portion of the surface of the solid substrate; The anti-counterfeiting products also include: The second anti-counterfeiting coating covers another part of the surface of the solid substrate. The second anti-counterfeiting coating is an anti-fog but non-frost-resistant coating, which is prepared by the following steps: an aqueous solution of a polymer containing hydroxyl groups in the main chain or side chain with a mass concentration of 1% to 50% is mixed with an organosilane reagent and a polymer containing carboxyl groups in the main chain or side chain to obtain a polymer crosslinked liquid. The polymer crosslinked liquid is defoamed and the precipitate is removed, and then coated on the solid substrate and dried to obtain an anti-fog but non-frost-resistant coating with a network structure and controllable crosslinking degree. The crosslinking degree of the polymer containing hydroxyl groups in the main chain or side chain is 5% to 80%, and the mass concentration of uncrosslinked polymers containing hydroxyl groups in the main chain or side chain of the polymer crosslinked liquid is less than 2%.

13. The anti-counterfeiting product according to claim 6, characterized in that, The solid substrate is selected from inorganic glass, polymer sheets or films, and entry / exit documents.

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