Structural chromogenic functional coating liquid, structural chromogenic functional film and manufacturing method of structural chromogenic functional film

Abstract

The invention relates to the field of coatings, in particular to a structural chromogenic functional coating liquid, a structural chromogenic functional film and a manufacturing method of the structural chromogenic functional film, and the structural chromogenic functional film comprises a structural chromogenic layer; the structural chromogenic layer is a resin layer comprising nano-structural chromogenic particles; and the structural chromogenic functional film is a film layer with ductility. According to the invention, the nano-structure color-producing particles are dispersed in the resin layer, so that the nano-structure color-producing particles for color development can still be relatively uniformly distributed in the structural color-producing functional film at effective intervals even if the structural color-producing functional film is extended and stretched in the subsequent use process; therefore, sufficient scattering intensity is guaranteed, the color development uniformity of the functional film is greatly improved, and meanwhile, the problem of chromatic aberration of the structural chromogenic functional film before and after stretching is greatly improved.

Description

Technical Field

[0001] The invention relates to the field of coatings, and in particular to a structural color-forming functional coating liquid, a structural color-forming functional film and a manufacturing method thereof. Background Art

[0002] At present, the decorative films on the market are mainly color-changing films, which can present different colors and effects when attached to the surface of the decorated object. However, the colors of the color-changing films on the market are still mostly realized by traditional colored dyes or pigments, which cannot avoid the problems of high production cost, complex production process, serious pollution and poor light fastness.

[0003] In order to solve the above problems, people began to rely on nanostructured color-producing materials to provide a bright appearance. Nanostructured color-producing materials are colors produced by the interaction between the microscopic physical structure of nanomaterials and visible light, which includes scattering, interference or diffraction. At present, nanostructured color-producing materials are mostly directly set on the surface of the structure to be colored, and then covered with other film layers for protection. However, such nano-film layers have poor color rendering effects in functional film layers that require a certain degree of stretching and deformation, and often cause problems such as uneven color rendering and color cast.

[0004] Therefore, how to solve the problem of uneven color and color cast in the process of film deformation of the nanostructured color-forming materials in the prior art is an urgent problem to be solved by those skilled in the art. Summary of the invention

[0005] The purpose of the present invention is to provide a structural color-forming functional coating liquid, a structural color-forming functional film and a method for manufacturing the same, so as to solve the problem of uneven color and color cast in the process of deformation of the nanostructured color-forming material in the prior art.

[0006] In order to solve the above technical problems, the present invention provides a structural chromogenic functional film, comprising a structural chromogenic layer;

[0007] The structural chromogenic layer is a resin layer including nanostructured chromogenic particles;

[0008] The structural color-forming functional film is a film layer with ductility.

[0009] Optionally, in the structural chromogenic functional film, when the structural chromogenic functional film is stretched to a target elongation, a corresponding changed color difference value of the structural chromogenic functional film is less than a preset tolerance color difference value;

[0010] And / or a base color layer is arranged below the structural color-producing layer.

[0011] Optionally, in the structural chromogenic functional film, when the structural chromogenic functional film is stretched to a target elongation, the spacing between the nanostructured chromogenic particles in the structural chromogenic layer does not exceed the particle size of the nanostructured chromogenic particles.

[0012] Optionally, in the structural color-producing functional film, the nanostructured color-producing particles include an organic group covering layer.

[0013] Optionally, in the structural color-forming functional film, the resin layer includes at least one of a polyvinyl chloride resin layer, a polyurethane resin layer, a polyacrylate resin layer and a fluororesin layer;

[0014] and / or

[0015] The nanostructured color-producing particles include at least one of Cu2O particles, CuO particles, SiO2 particles, Al2O3 particles, ZrO2 particles, V2O5 particles, ZnO particles, CaS particles, CuS particles, Cu2S particles, CdS particles, CeO2 particles, ZnS particles, and TiO2 particles;

[0016] and / or

[0017] The particle size of the nanostructured color-forming particles ranges from 100 nanometers to 700 nanometers, including end points; and the particle size distribution index of the nanostructured color-forming particles is not less than 95%.

[0018] A method for manufacturing a structural chromogenic functional film, comprising:

[0019] The nanostructured color-forming particles, resin and diluent are mixed to obtain a structured color-forming coating liquid;

[0020] Applying the structured color-generating coating liquid onto a substrate;

[0021] The substrate coated with the structural color-forming coating liquid is subjected to heat treatment to obtain a structural color-forming functional film including a structural color-forming layer; the structural color-forming functional film is a film layer with ductility.

[0022] Optionally, in the method for manufacturing the structural color-forming functional film, the step of mixing the nanostructured color-forming particles, the resin and the diluent to obtain the structural color-forming coating liquid comprises:

[0023] The nanostructured color-forming particles, resin, additives and diluent are mixed to obtain a structured color-forming coating liquid; the additives include at least one of a plasticizer, a heat stabilizer, a light absorber, a light stabilizer, a leveling agent, a dispersant, and a viscosity-increasing and viscosity-reducing additive;

[0024] And / or, before mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating solution, the method further comprises:

[0025] An organic group covering layer is arranged on the surface of the nanostructured color-forming particles through chemical coupling agent modification and / or adsorption modification and / or self-assembly modification.

[0026] Optionally, in the method for manufacturing the structural color-forming functional film, the step of mixing the nanostructured color-forming particles, the resin and the diluent to obtain the structural color-forming coating liquid comprises:

[0027] Mixing and dispersing the nanostructured color-forming particles with a first diluent to obtain a first mixture; the first diluent is a polar diluent;

[0028] Mixing and dispersing the resin and the second diluent to obtain a second mixture;

[0029] The first mixture and the second mixture are mixed and dispersed to obtain a structured color-producing coating liquid.

[0030] Optionally, in the method for manufacturing the structural color-forming functional film, before mixing the nanostructured color-forming particles, the resin and the diluent to obtain the structural color-forming coating solution, the method further comprises:

[0031] An organic group covering layer is arranged on the surface of the nanostructured color-forming particles through chemical coupling agent modification and / or adsorption modification and / or self-assembly modification.

[0032] Optionally, in the method for manufacturing the structural color-forming functional film, before mixing the nanostructured color-forming particles, the resin and the diluent to obtain the structural color-forming coating solution, the method further comprises:

[0033] When the ratio of the spacing between the nanostructured color-forming particles and the particle size of the nanostructured color-forming particles is calculated to be a first preset value, the volume ratio of the nanostructured color-forming particles to the resin; the product of the first preset value and the target elongation of the structured color-forming functional film does not exceed 1;

[0034] Determining the mass ratio of the nanostructured color-forming particles to the resin according to the density of the nanostructured color-forming particles, the density of the resin and the volume ratio;

[0035] Accordingly, the step of mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating liquid comprises:

[0036] The diluent, the nanostructured color-producing particles in the mass ratio and the resin are mixed to obtain a structured color-producing coating liquid.

[0037] A structural color-generating functional coating liquid comprises a diluent, nano-structured color-generating particles and a resin.

[0038] The structural color-forming functional film provided by the present invention comprises a structural color-forming layer; the structural color-forming layer is a resin layer comprising nanostructured color-forming particles; the structural color-forming functional film is a ductile film layer. The present invention disperses the nanostructured color-forming particles in the resin layer, thereby ensuring that in the subsequent use process, even if the structural color-forming functional film is stretched and stretched, the nanostructured color-forming particles used for color development can still be relatively uniformly and effectively distributed in the structural color-forming functional film to ensure that sufficient scattering intensity is obtained, thereby greatly improving the color development uniformity of the functional film, and at the same time greatly improving the color difference problem of the structural color-forming functional film before and after stretching. The present invention also provides a method for manufacturing a structural color-forming functional film and a structural color-forming functional coating liquid having the above-mentioned beneficial effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0040] FIG1 is a schematic structural diagram of a specific embodiment of a structural color-forming functional film provided by the present invention;

[0041] FIG2 is a schematic diagram of a partial structure of a specific embodiment of a structural color-forming functional film provided by the present invention;

[0042] FIG3 is a schematic flow chart of a specific embodiment of the method for manufacturing the structural color-forming functional film provided by the present invention.

[0043] In the figure, it includes 10-structured color-producing layer, 20-base color layer, 30-transparent layer, 11-resin, and 12-nanostructured color-producing particles. DETAILED DESCRIPTION

[0044] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific implementation methods. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0045] The core of the present invention is to provide a structural chromogenic functional film, a structural schematic diagram of a specific embodiment of which is shown in FIG1 , referred to as specific embodiment 1, comprising a structural chromogenic layer 10;

[0046] The structural color-producing layer 10 is a resin layer including nanostructured color-producing particles 12;

[0047] The structural color-forming functional film is a film layer with ductility.

[0048] The nanostructured color-generating particles 12 are suspended in the resin layer. Of course, the more uniform the distribution of the nanostructured color-generating particles 12 in the resin layer, the better.

[0049] Furthermore, when the structural chromogenic functional film is stretched to a target elongation, a corresponding changed color difference value of the structural chromogenic functional film is less than a preset tolerable color difference value.

[0050] The changed color difference value is the color difference value of the structural color-forming functional film before stretching and when stretched to the target elongation. In this preferred embodiment, the color difference value of the structural color-forming functional film before and after stretching is further limited to a reasonable range (less than the tolerable color difference value), so that the color of the structural color-forming functional film does not change significantly even after stretching, thereby improving the color stability of the structural color-forming functional film. Preferably, the tolerable color difference value is not greater than 3.

[0051] As a specific implementation, a base color layer 20 is disposed below the structural color-producing layer 10 .

[0052] The base color layer 20 cooperates with the structural color layer 10 to enhance the masking effect of the structural color functional film and improve the color development effect of the structural color functional film. The base color layer 20 can be a black layer, a white layer or a color layer, which is not limited in the present invention. More preferably, the base color layer 20 is at least any one of a solid color layer, an effect layer, and an effect solid color layer.

[0053] Furthermore, when the structural chromogenic functional film is stretched to a target elongation, the spacing between the nanostructured chromogenic particles 12 in the structural chromogenic layer 10 does not exceed the particle size of the nanostructured chromogenic particles 12;

[0054] The target elongation does not exceed 500%.

[0055] The target elongation should be set according to the elongation of the structural color-forming functional film during use, that is, the target elongation is the elongation of the structural color-forming functional film during operation. In this way, even if the structural color-forming functional film is stretched during use, the spacing between the nanostructured color-forming particles 12 still does not exceed the particle size of the nanostructured color-forming particles 12. Under this condition, a proximity effect can be generated between the particles, and the scattering intensity will increase, thereby achieving a better color rendering effect. Of course, there are other similar effects. For example, when the particles are arranged periodically, a photonic band gap can be formed, thereby preventing the propagation of light of certain frequencies and producing specific colors; and when the particles are arranged randomly and disorderly, the nanoparticles can produce a wide range of colors through multi-path scattering.

[0056] Furthermore, the nanostructured color-producing particle 12 includes an organic group covering layer.

[0057] Since the nanostructured color-forming particles 12 are of an inorganic compound structure and have a relatively high density, it has long been difficult to evenly disperse them in polymer coatings. In order to further increase the uniformity of the dispersion of the nanostructured color-forming particles 12 in the coating and prevent the nanostructured color-forming particles 12 from settling in the coating, the preferred embodiment chemically modifies the surface of the nanostructured color-forming particles 12 so that the surface is coated with a layer of organic groups to improve its compatibility with the resin 11, further enhancing its uniformity of dispersion in the coating, and effectively preventing the nanostructured color-forming particles 12 from settling and affecting the color realization effect during storage and processing. The schematic diagram of the dispersion distribution of the nanostructured color-forming particles 12 in the resin 11 is shown in Figure 2.

[0058] As a specific implementation, the resin layer includes at least one of a polyvinyl chloride resin layer, a polyurethane resin layer, a polyacrylate resin layer and a fluororesin layer;

[0059] and / or

[0060] The nanostructured color-generating particles 12 include at least one of Cu2O particles, CuO particles, SiO2 particles, Al2O3 particles, ZrO2 particles, V2O5 particles, ZnO particles, CaS particles, CuS particles, Cu2S particles, CdS particles, CeO2 particles, ZnS particles, and TiO2 particles;

[0061] and / or

[0062] The particle size of the nanostructured color-forming particles 12 ranges from 100 nanometers to 700 nanometers, including end points; and the particle size distribution index of the nanostructured color-forming particles 12 is not less than 95%.

[0063] The above materials and data ranges are all the best ranges after a large number of theoretical calculations and actual tests. Of course, they can also be adjusted accordingly according to the actual situation, which will not be elaborated in this invention.

[0064] As the nanostructured color - generating particles 12 that can generate structural color, the basis for their ability to generate color lies in that the nanoparticle grains as structural units have strong electromagnetic resonance characteristics. According to Mie scattering theory, the scattering intensity of a single dielectric nanoparticle depends on its electric resonance and magnetic resonance coefficients, and these coefficients are in turn affected by the refractive index of the nanomaterial itself. Specifically, these coefficients depend on the refractive index of the particle sphere, the refractive index of the medium, as well as the wavelength of the incident light and the size of the dielectric particle sphere. The higher the refractive index, the higher the intensity of the electromagnetic resonance. Silicon, due to its relatively high refractive index (n > 3), has become a relatively common dielectric nanomaterial and has been deeply studied. There are research reports that silicon nanoparticles with different diameters show strong electromagnetic resonance effects in the visible light region. And in the resonance scattering of silicon nanoparticles, magnetic dipole and electric dipole dominate. The lowest - order peak in the scattering spectrum corresponds to the magnetic dipole mode, showing significant size dependence. The relationship between the position of the reflection peak and the diameter of the microsphere is approximately λ = nd, where λ represents the position of the reflection peak, n is the refractive index of the nanostructured color - generating particles 12, and d is the diameter of the nanostructured color - generating particles 12.

[0065] Although there are many studies on silicon - based dielectric nanoparticles, due to the preparation of silicon nanoparticles relying on methods such as laser etching and chemical vapor deposition, these methods are expensive in equipment and long in preparation cycle, resulting in high cost and low efficiency. Different from silicon - based dielectric nanoparticles, dielectric nanospheres with medium refractive indices (1.7 < n < 3.0), such as TiO2, Cu2O, CdS, ZnS, and ZnO, can be synthesized in batches by chemical methods, which has become a new direction for current research on the electromagnetic resonance of dielectric nanoparticles. Theoretical calculations show that when the diameter of dielectric nanospheres with medium refractive indices is greater than 200 nm, they have strong magnetic resonance effects. Additionally, different from high - refractive - index dielectric nanospheres, the electric dipole and magnetic dipole resonances of medium - refractive - index nanospheres overlap. This scattering characteristic has been further verified in the research on the scattering characteristics of various microspheres, such as TiO2 and Cu2O nanosphere particles. The measured scattering spectrum of Cu2O nanosphere particles is similar to the calculated scattering spectrum of medium - refractive - index nanospheres (n ~ 2.7). At the same time, as the diameter increases, the scattering peaks of these Cu2O nanosphere particles show an obvious red - shift. Similarly, TiO2 nanospheres also show the same trend, based on which the material selection of the nanostructured color - generating particles 12 in this invention can be carried out.

[0066] Therefore, dielectric nanosphere particles with a medium refractive index (1.7 < n < 3) have more application advantages due to their low cost and easy availability. The present invention selects dielectric nanostructured color-forming particles 12 with a medium refractive index (Cu2O particles, CuO particles, SiO2 particles, Al2O3 particles, ZrO2 particles, V2O5 particles, ZnO particles, CaS particles, CuS particles, Cu2S particles, CdS particles, CeO2 particles, ZnS particles, TiO2 particles, etc.) to control the particle size of the nano-color-forming material to achieve scattering of visible light of different wavelengths, thereby adjusting the different colors of the decorative film.

[0067] More preferably, a transparent layer 30 is further provided on the surface of the structural chromogenic layer 10 ; the transparent layer 30 can be a bright transparent layer 30 or a matte transparent layer 30 ; the transparent layer 30 can be a colorless transparent layer 30 or a colored transparent layer 30 .

[0068] Preferably, the target elongation at break of the structural chromogenic functional film is 100% to 500%; more preferably, the elongation at break of the structural chromogenic functional film is 200% to 400%.

[0069] The structural color-forming functional film provided by the present invention comprises a structural color-forming layer 10; the structural color-forming layer 10 is a resin layer comprising nanostructured color-forming particles 12; and the structural color-forming functional film is a film layer with ductility. The present invention disperses the nanostructured color-forming particles 12 in the resin layer, thereby ensuring that in the subsequent use process, even if the structural color-forming functional film is stretched, the nanostructured color-forming particles 12 for color development can still be relatively uniformly and effectively distributed in the structural color-forming functional film to ensure that sufficient scattering intensity is obtained, thereby greatly improving the color development uniformity of the functional film, and at the same time greatly improving the color difference problem of the structural color-forming functional film before and after stretching.

[0070] The present invention also provides a method for manufacturing a structural color-forming functional film, a flow diagram of a specific implementation method thereof is shown in FIG3 , which is referred to as specific implementation method 2, and comprises:

[0071] S101: Mix the nanostructured color-producing particles 12, the resin 11 and the diluent to obtain a structured color-producing coating liquid.

[0072] S102: coating the structured color-generating coating liquid onto a substrate.

[0073] S103: heat-treating the substrate coated with the structural chromogenic coating liquid to obtain a structural chromogenic functional film including a structural chromogenic layer 10; the structural chromogenic functional film is a film layer with ductility.

[0074] It should be noted that the substrate in this step may be the internal structure of the structural color-forming functional film, which is retained after the heat treatment step. For example, the substrate may be the base color layer 20. Of course, the substrate may not be a part of the structural color-forming functional film. After the heat treatment is completed, the structural color-forming layer 10 can be removed from the substrate.

[0075] The method for manufacturing the structural chromogenic functional film in this specific embodiment corresponds to the structural chromogenic functional film mentioned above. Please refer to the above text for technical details, and the present invention will not be repeated here.

[0076] Preferably, the step of mixing the nanostructured color-producing particles 12, the resin 11 and the diluent to obtain the structured color-producing coating liquid comprises:

[0077] The nanostructured color-forming particles 12, the resin 11, the additives and the diluent are mixed to obtain a structured color-forming coating liquid; the additives include at least one of a plasticizer, a heat stabilizer, a light absorber, a light stabilizer, a leveling agent, a dispersant, a viscosity-increasing agent and a viscosity-reducing agent.

[0078] In this preferred embodiment, the above-mentioned auxiliary agent and the diluent are mixed with the nanostructured color-producing particles 12 and the resin 11 to achieve a better mixing effect. The specific type of auxiliary agent added can be selected according to actual conditions.

[0079] As a preferred embodiment, the step of mixing the nanostructured color-producing particles 12, the resin 11 and the diluent to obtain the structured color-producing coating liquid comprises:

[0080] A1: The nanostructured color-producing particles 12 are mixed and dispersed with a first diluent to obtain a first mixture; the first diluent is a polar diluent.

[0081] The first diluent includes at least one of alkyl alcohol, alkyl ketone, water, DMF (N,N-dimethylformamide), DMAc (N,N-dimethylacetamide), NMP (N-methylpyrrolidone), and THF (tetrahydrofuran).

[0082] The nanostructured color-forming particles 12 have better compatibility with the polar diluent. After being mixed with the polar diluent, the nanostructured color-forming particles 12 can obtain better dispersibility, that is, the dispersion is more uniform.

[0083] A2: The resin 11 is mixed and dispersed with the second diluent to obtain a second mixture.

[0084] The second diluent includes at least one of alkyl esters, alkyl substituted benzenes, alkyl ketones, and organic ethers.

[0085] A3: The first mixture and the second mixture are mixed and dispersed to obtain a structured color-producing coating liquid.

[0086] In this preferred embodiment, the nanostructured color-producing particles 12 are not directly mixed with the resin 11 and the diluent. Instead, the nanostructured particles 12 are first made into a separate dispersion liquid. The purpose is to first disperse the nanostructured particles in the solution into a uniform and non-aggregate state, and then disperse them into the resin 11 coating liquid, which is beneficial for the nanospheres to form a uniform and non-aggregate dispersed state in the overall resin 11 coating liquid.

[0087] Furthermore, before the nanostructured color-producing particles 12, the resin 11 and the diluent are mixed to obtain the structured color-producing coating solution, the method further includes:

[0088] An organic group covering layer is provided on the surface of the nanostructured color-producing particles 12 by chemical coupling agent modification and / or adsorption modification and / or self-assembly modification.

[0089] In this preferred embodiment, an organic group covering layer is provided on the surface of the nanostructured color-forming particles 12 by at least one of the above three surface modification methods. By introducing new functional groups (such as alkyl, fluoro, amino, epoxy, etc.) on the surface, the chemical properties of the surface of the nanospheres are changed, and the compatibility between the nanospheres and the resin 11 is improved, thereby improving the dispersion performance of the nanospheres in the coating liquid. Furthermore, it is preferred to adopt chemical coupling agent modification to provide the organic group covering layer. The chemical coupling agent modification is to react the silane coupling agent with -OH and -SH on the surface of the nanospheres to form a covalent bond or a hydrogen bond, thereby introducing new functional groups on the surface. The chemical coupling agent modification is easy to operate, and the amount of the coupling agent added can be controlled to control the number of functional groups connected to the surface of the nanostructured color-forming particles 12.

[0090] As another preferred embodiment, before the nanostructured color-producing particles 12, the resin 11 and the diluent are mixed to obtain the structured color-producing coating liquid, the method further comprises:

[0091] B1: When the ratio of the spacing between the nanostructured color-forming particles 12 and the particle size of the nanostructured color-forming particles 12 is calculated to be a first preset value, the volume ratio of the nanostructured color-forming particles 12 to the resin 11; the product of the first preset value and the target elongation of the structural color-forming functional film does not exceed 1.

[0092] B2: Determine the mass ratio of the nanostructured color-forming particles 12 to the resin 11 according to the density of the nanostructured color-forming particles 12 , the density of the resin 11 , and the volume ratio.

[0093] Since the target volume ratio is known and the density of the nanostructured color-forming particles 12 and the density of the resin 11 are known, the mass ratio of the nanostructured color-forming particles 12 to the resin 11 at the volume ratio can be calculated.

[0094] Accordingly, the step of mixing the nanostructured color-producing particles 12, the resin 11 and the diluent to obtain the structured color-producing coating liquid comprises:

[0095] B3: Mix the diluent, the nanostructured color-producing particles 12 and the resin 11 in the mass ratio to obtain a structured color-producing coating liquid.

[0096] From the description of the structural color-forming functional film above, it can be seen that the first preset value corresponds to the target elongation. In other words, according to the limitation given in this step, even if the structural color-forming functional film is stretched to reach the target elongation, the spacing between adjacent nanostructure color-forming particles 12 will not exceed the particle size of the structural color-forming particles. By calculating the mass ratio corresponding to the target elongation through volume and density, and then allocating the raw materials in production according to the mass ratio, the preparation process can be greatly simplified and the production efficiency can be improved.

[0097] Specifically, it can be calculated by the volume fraction of the nanostructured color-forming particles 12 in the structural color-forming functional film, that is, the ratio of the volume of the nanostructured color-forming particles 12 to the volume of the cube formed by the particle size of the nanostructured color-forming particles 12 + the distance between the nanostructured color-forming particles 12; specifically, the maximum volume fraction is reached when the distance between the nanostructured color-forming particles 12 is 0, and the minimum volume fraction is reached when the distance between the nanospheres is the diameter of the nanospheres. Specifically, it can be estimated by the following formulas (1) to (3):

[0098] Φ=V ball / V cube ; (1)

[0099] V ball =4πr 3 / 3; (2)

[0100] V cube =(2r+l) 3 ; (3)

[0101] Where Φ represents the volume fraction of the structured color-forming functional film occupied by the nanostructured color-forming particles 12; V ball represents the volume of the nanostructured color-producing particle 12; V cube represents the cubic volume occupied by a single nanostructured color-forming particle 12 when it is distributed in space; r represents the radius of the nanostructured color-forming particle 12; l represents the spacing between the nanostructured color-forming particles 12; when l is 0, the volume fraction of the nanostructured color-forming particle 12 in the structural color-forming functional film reaches the maximum value; when l=2r, the volume fraction of the nanostructured color-forming particle 12 in the structural color-forming functional film reaches the theoretical minimum value;

[0102] Furthermore, the diluent is a mixed diluent with a boiling point gradient to control the volatilization rate of the diluent during the drying process of the coating so as to obtain a dry paint film with uniform distribution of nanostructured color-producing particles 12; further, when preparing the paint film of the color-producing coating involved in the present invention, the drying temperature also adopts a gradient design to further optimize the drying rate of the coating so as to obtain a dry paint film with uniform distribution of nanostructured color-producing particles 12; the structural color-producing coating involved in the present invention has a uniform three-dimensional spatial distribution of nanostructured color-producing particles 12 in the coating state and in the dry paint film formed after the coating is dried, so it can show uniform color and appearance in both normal and stretched states.

[0103] The manufacturing method of the structural color-forming functional film provided by the present invention comprises the following steps: mixing nanostructured color-forming particles 12, resin 11 and diluent to obtain a structural color-forming coating liquid; applying the structural color-forming coating liquid to a substrate; and heat-treating the substrate coated with the structural color-forming coating liquid to obtain a structural color-forming functional film including a structural color-forming layer 10; the structural color-forming functional film is a ductile film layer. The present invention disperses the nanostructured color-forming particles 12 in the resin layer, thereby ensuring that in the subsequent use process, even if the structural color-forming functional film is stretched and stretched, the nanostructured color-forming particles 12 for color development can still be relatively uniformly and effectively distributed in the structural color-forming functional film to ensure that sufficient scattering intensity is obtained, thereby greatly improving the color development uniformity of the functional film, and at the same time greatly improving the color difference problem of the structural color-forming functional film before and after stretching.

[0104] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0105] The present invention also provides a structural chromogenic functional coating liquid, comprising a diluent, nanostructured chromogenic particles and a resin. The structural chromogenic functional coating liquid can also be added with corresponding functional additives according to actual needs, and the additives include at least one of a plasticizer, a heat stabilizer, a light absorber, a light stabilizer, a leveling agent, a dispersant, and a viscosity increasing and viscosity reducing additive, which is not limited by the present invention. The structural chromogenic functional coating liquid provided by the present invention can obtain the structural chromogenic functional film mentioned above after being treated. The specific method can refer to the manufacturing method of the structural chromogenic functional film mentioned above. The structural chromogenic functional coating liquid in this specific embodiment can be considered as the structural chromogenic coating liquid in the manufacturing method of the structural chromogenic functional film. Please refer to the above text for details, and the present invention will not repeat them here.

[0106] Several specific embodiments of the method for manufacturing the structural color-forming functional film are given below.

[0107] Example 1, preparation of structural color-forming PVC coating liquid;

[0108] 50g of nano cuprous oxide and 100g of isopropanol; weigh the nano cuprous oxide and isopropanol according to the above ratio, then add the nano ferrous oxide to the isopropanol, and mix them evenly by ultrasonic to obtain a first mixed solution;

[0109] 100g PVC paste resin, 40g plasticizer, 5g heat stabilizer, 1.5g light stabilizer, 20g xylene, 30g isopentyl acetate, 120g first mixture; weigh the above composition except the first mixture according to the proportion, mix and stir at 200r / min for 2h to make it fully mixed, then add the above first mixture according to the proportion, then 200r / min, continue mixing and stirring for 1h to obtain the nanostructured color-forming coating.

[0110] Example 2: Surface modification of structural chromogenic nanospheres;

[0111] 5 g of nano cuprous oxide, 1.48 g of silane coupling agent (3-aminopropyltriethoxysilane), 50 mL of toluene, and 3.5 mL of deionized water; add the silane coupling agent 3-aminotriethoxysilane to toluene, mix well, and then add deionized water to obtain a mixed solution; disperse the nano ferrous oxide into the mixed solution during mechanical stirring, and continue stirring for 5 hours; filter, wash with water, and dry at 100°C to obtain modified nanoparticles.

[0112] Example 3, preparation process of color-changing functional film;

[0113] The PVC transparent layer 30 coating is evenly coated on the substrate film, and after being baked in an oven at 80°C for 2 minutes, the oven temperature is gradually increased to 200°C and kept at 200°C for 3 minutes, and then the temperature is lowered to obtain the coating of the transparent layer 30. The coating method can be selected from blade coating, roller coating, and spray coating, and the specific coating method is not limited; the coating thickness is set according to different needs.

[0114] The structured chromogenic layer coating is uniformly coated on the surface of the transparent layer 30, and after being baked in an oven at 80°C for 2 minutes, the oven temperature is gradually increased to 200°C and kept at 200°C for 3 minutes, and then the temperature is lowered to obtain the structured chromogenic layer containing the transparent layer. The coating method can be selected from blade coating, roller coating, and spray coating, and the specific coating method is not limited; the coating thickness is set according to different needs.

[0115] According to the needs, the surface of the structural color-forming layer is uniformly coated with the prepared white, black, color or special effect PVC base color coating, and after baking in an oven at 80°C for 2 minutes, the oven is gradually heated to 200°C and kept at 200°C for 3 minutes, and then cooled to obtain a base film of the structural color-forming functional film containing the base color layer 20. The white, black, color or special effect base color is selected according to different target color schemes and presentation effects; the coating method can be selected by scraping, rolling or spraying, and the specific coating method is not limited; the coating thickness is set according to different needs.

[0116] Table 1 shows the preparation data of some structural color-producing functional films with different colors for reference.

[0117] Table 1

[0118] Serial number Color Effects Types of Nanomaterials Nanoparticle size (nm) Nanoparticle concentration Transparent layer effect Transparent layer thickness (μm) Thickness of structural chromophore layer (μm) Base layer Thickness of base layer (μm) 1 Highlight Green <![CDATA[Cu2O]]> 210 13% Highlight Transparent 20 20 black 90 2 Matte green <![CDATA[Cu2O]]> 210 13% Matte transparent 20 20 black 90 3 Highlight Orange <![CDATA[Cu2O]]> 210 13% Red transparent 20 20 black 90 4 Light Green <![CDATA[Cu2O]]> 210 13% Highlight Transparent 20 20 White 90 5 blue <![CDATA[Cu2O]]> 210 13% Highlight Transparent 20 20 blue 90 6 Metallic effect green <![CDATA[Cu2O]]> 210 13% Highlight Transparent 20 20 Metallic Black 90 7 Highlight blue ZnS 240 9% Highlight Transparent 20 20 black 90 8 Highlight red <![CDATA[CeO2]]> 350 9% Highlight Transparent 20 20 black 90 9 Highlight Purple <![CDATA[Cu2O]]> 250 12% Highlight Transparent 20 20 black 90 10 Highlight Purple ZnO 260 18% Highlight Transparent 20 20 black 90 11 Highlight Orange <![CDATA[Cu2O]]> 270 13% Highlight Transparent 20 20 black 90 12 Highlight Green ZnS 240 / 265=2 / 1 9% Highlight Transparent 20 20 black 90 13 Highlight Green <![CDATA[Modified Cu2O]]> 210 13% Highlight Transparent 20 20 black 90

[0119] It should be noted that, in this specification, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "comprise", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the statement "comprises a ..." does not exclude the presence of other identical elements in the process, method, article or device including the element.

[0120] The above is a detailed introduction to the structural color-forming functional coating liquid, structural color-forming functional film and manufacturing method thereof provided by the present invention. Specific examples are used herein to illustrate the principle and implementation method of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A structural chromogenic functional film, characterized in that: including a structural chromophore layer; The structural chromogenic layer is a resin layer including nanostructured chromogenic particles; The structural color-forming functional film is a film layer with ductility.

2. The structural chromogenic functional film according to claim 1, characterized in that: When the structural chromogenic functional film is stretched to a target elongation, the corresponding changed color difference value of the structural chromogenic functional film is less than a preset tolerance color difference value; And / or a base color layer is arranged below the structural color-producing layer.

3. The structural chromogenic functional film according to claim 2, characterized in that: When the structural color-producing functional film is stretched to a target elongation, the spacing between the nanostructured color-producing particles in the structural color-producing layer does not exceed the particle size of the nanostructured color-producing particles.

4. The structural chromogenic functional film according to claim 1, characterized in that: The nanostructured color-producing particles include a covering layer of organic groups.

5. The structural chromogenic functional film according to claim 1, characterized in that: The resin layer includes at least one of a polyvinyl chloride resin layer, a polyurethane resin layer, a polyacrylate resin layer and a fluororesin layer; and / or The nanostructured color-producing particles include at least one of Cu2O particles, CuO particles, SiO2 particles, Al2O3 particles, ZrO2 particles, V2O5 particles, ZnO particles, CaS particles, CuS particles, Cu2S particles, CdS particles, CeO2 particles, ZnS particles, and TiO2 particles; and / or The particle size of the nanostructured color-forming particles ranges from 100 nanometers to 700 nanometers, including end points; and the particle size distribution index of the nanostructured color-forming particles is not less than 95%.

6. A method for manufacturing a structural chromogenic functional film, characterized in that: include: Mixing nanostructured color-forming particles, resin and diluent to obtain a structured color-forming coating solution; Applying the structured color-generating coating liquid onto a substrate; The substrate coated with the structural color-forming coating liquid is subjected to heat treatment to obtain a structural color-forming functional film including a structural color-forming layer; the structural color-forming functional film is a film layer with ductility.

7. The method for manufacturing a structural chromogenic functional film according to claim 6, characterized in that: The step of mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating liquid comprises: The nanostructured color-forming particles, resin, additives and diluent are mixed to obtain a structured color-forming coating liquid; the additives include at least one of a plasticizer, a heat stabilizer, a light absorber, a light stabilizer, a leveling agent, a dispersant, and a viscosity-increasing and viscosity-reducing additive; And / or, before mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating solution, the method further comprises: An organic group covering layer is arranged on the surface of the nanostructured color-forming particles through chemical coupling agent modification and / or adsorption modification and / or self-assembly modification.

8. The method for manufacturing a structural chromogenic functional film according to claim 6, characterized in that: The step of mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating liquid comprises: Mixing and dispersing the nanostructured color-forming particles with a first diluent to obtain a first mixture; the first diluent is a polar diluent; Mixing and dispersing the resin and the second diluent to obtain a second mixture; The first mixture and the second mixture are mixed and dispersed to obtain a structured color-producing coating liquid.

9. The method for manufacturing a structural chromogenic functional film according to any one of claims 6 to 8, characterized in that: Before mixing the nanostructured color-forming particles, the resin and the diluent to obtain the structured color-forming coating solution, the method further comprises: When the ratio of the spacing between the nanostructured color-forming particles and the particle size of the nanostructured color-forming particles is calculated to be a first preset value, the volume ratio of the nanostructured color-forming particles to the resin; the product of the first preset value and the target elongation of the structured color-forming functional film does not exceed 1; Determining the mass ratio of the nanostructured color-forming particles to the resin according to the density of the nanostructured color-forming particles, the density of the resin and the volume ratio; Accordingly, the step of mixing the nanostructured color-producing particles, the resin and the diluent to obtain the structured color-producing coating liquid comprises: The diluent, the nanostructured color-producing particles in the mass ratio and the resin are mixed to obtain a structured color-producing coating liquid.

10. A structural color-forming functional coating liquid, characterized in that: It includes diluent, nanostructured color-producing particles and resin.

Images