Liquid crystal film with intelligent information encryption function, method for manufacturing the same, and use

Abstract

Regarding the technology of functional liquid crystal materials, a liquid crystal film having an intelligent information encryption function, a method for manufacturing the same, and its use are disclosed. [Solution] The liquid crystal film includes two parallel transparent substrates and a composite functional layer located between the transparent substrates. The composite functional layer includes a honeycomb polymer matrix and liquid crystals filling the pores of the polymer matrix. The liquid crystals have a polymer network, and because the distribution density of the polymer network differs in different regions of the liquid crystal film, the liquid crystal film has an information pattern that reversibly changes, disappearing (or appearing) when an electric field is applied and reappearing (or disappearing) after the electric field is cut off, or an information pattern that reversibly changes, disappearing (or appearing) at low temperatures and reappearing (or disappearing) at high temperatures. Because the distribution density of the polymer network differs in different regions of the liquid crystal film, and it has diverse responsiveness to electric fields, temperatures, magnetic fields, etc., various visual effects can be realized.

Description

[Technical Field]

[0001] This invention relates to the technology of functional liquid crystal materials, and more specifically to a liquid crystal film having an intelligent information encryption function, a method for manufacturing the same, and its use. [Background technology]

[0002] Currently, information-pattern controllable materials are typically realized using thermochromic, photochromic, and electrochromic materials. Common thermochromic materials include inorganic materials such as iodides, complexes, and organometallic compounds, and organic materials such as spiropyrans, phosphors, and polythiophenes. Photochromic materials include inorganic materials such as WO3, silver chloride, and silver bromide, and organic materials such as spiropyrans, fulgidic anhydrides, diarylethenes, spirooxazines, and azobenzenes. Electrochromic materials include metal oxides or hydrates such as WO3, MoO3, V2O5, Nb2O5, and TiO2, and platinum group (Pt, Ir, Os, Pd, Rh, Ru) metal oxides or hydrates, such as NiO and IrO x The materials include Rh2O3, and organic substances such as polythiophenes and their derivatives, viologens, tetrathiafulvalene, metal phthalocyanine compounds, polyaniline, polypyrrole, and polyethylenedioxythiophene. All of these materials can achieve reversible information patterning functionality under external field conditions. However, the above-mentioned color-changing materials have the problem of having a single function and being difficult to process into flexible films.

[0003] Liquid crystal materials are important organic thermochromic, photochromic, and electrochromic materials because they are responsive to external fields such as electric fields, magnetic fields, heat, pressure, and humidity. In thermochromic liquid crystal materials, temperature-sensitive color-changing devices, such as film thermometers, prepared by the smectic or crystalline-cholesteric phase transition of small molecule and polymer liquid crystal materials and the property of cholesteric liquid crystals to select reflection from incident light, are widely applied. In photochromic liquid crystal materials, a series of photochromic materials have been developed by incorporating azobenzene, molecular motors, and molecular switches into small molecule and polymer liquid crystals. In electrochromic liquid crystal materials, small molecule liquid crystals, polymer dispersed liquid crystals, and polymer stable liquid crystals are all very good electrochromic materials. All of the above liquid crystal materials can realize reversible information patterning functions in response to the action of an external field.

[0004] However, information-pattern controllable devices for preparing the above-mentioned liquid crystal materials have drawbacks that are difficult to overcome. In particular, small molecule liquid crystals are liquid, making it difficult to prepare large-area flexible films; polymer liquid crystals have high viscosity, making it difficult to uniformly orient large areas, making it difficult to process into large-area flexible films; and it is also difficult to switch patterns using the action of an external field. Polymer-stabilized liquid crystal (PSLC) films can achieve various patterns, but their polymer network content is low, usually less than 10 wt%, resulting in low peel strength between the two substrates and making it difficult to manufacture large-area flexible films. Polymer-dispersed liquid crystals (PDLCs) have a relatively high polymer matrix content, resulting in high peel strength between the two substrates and the ability to manufacture large-area flexible films, leading to a wide range of applications. However, the porous polymer matrix inside PDLCs cannot guide or stabilize the orientation of liquid crystal molecules, resulting in a single light control characteristic, and the film is usually in a light-scattering state, making it impossible to achieve various patterns.

[0005] Existing reversible information patterning products are no longer able to meet diverse consumer needs, making the development of new, controllable information patterning products an urgent necessity. [Overview of the Initiative]

[0006] The present invention provides a liquid crystal film having an intelligent information encryption function, a method for manufacturing the same, and a method for using the same, with the aim of solving the problems inherent in conventional liquid crystal information pattern controllable materials, such as the difficulty in film manufacturing, the difficulty in switching patterns, and the inability to achieve diverse patterning. To achieve the above objective, the present invention employs the following technical means.

[0007] In a first aspect of the present invention, a liquid crystal film having an intelligent information encryption function is provided, comprising two parallel transparent substrates and a composite functional layer located between the transparent substrates, wherein the composite functional layer comprises a honeycomb polymer matrix and liquid crystals filling the pores of the polymer matrix, and the liquid crystal has a polymer network, and the distribution density of the polymer network differs in different regions of the liquid crystal film, thereby providing a liquid crystal film having an information pattern that reversibly changes so as to disappear (or appear) when an electric field is applied and reappear (or disappear) after the electric field is cut off, or an information pattern that reversibly changes so as to disappear (or appear) at low temperatures and reappear (or disappear) at high temperatures.

[0008] In some embodiments, the raw materials for the composite functional layer include, by weight, 5 wt% to 60 wt% of a flexible polymerizable monomer, 0.5 wt% to 15 wt% of a rod-shaped photopolymerizable monomer, 20 wt% to 94.4 wt% of a liquid crystal, 0.1 wt% to 5 wt% of an initiator, and spacer particles in a quantity of 0.1 wt% to 2 wt% of the sum of the quantities of the flexible polymerizable monomer, rod-shaped photopolymerizable monomer, liquid crystal mixture, and initiator.

[0009] In some embodiments, the flexible polymerizable monomer comprises at least one of a flexible photopolymerizable monomer or a flexible thermal polymerizable monomer, wherein the flexible photopolymerizable monomer is subjected to radical polymerization or cationic polymerization under ultraviolet irradiation, and the flexible thermal polymerizable monomer is subjected to thermal polymerization under heating conditions. The rod-shaped photopolymerizable monomer is subjected to radical polymerization or cationic polymerization under ultraviolet irradiation. The liquid crystal is a positive-type liquid crystal, a negative-type liquid crystal, or a dual-frequency driven liquid crystal. The initiator is a radical initiator, a cationic photoinitiator, or a thermal initiator. The spacer particles are microspheres of styrene or silicon dioxide, with a diameter of 2 μm to 100 μm.

[0010] In some embodiments, the flexible photopolymerizable monomer comprises at least one of acrylate monomers, olefin monomers, vinyl ether monomers, or epoxy monomers. The flexible, thermopolymerizable monomer comprises at least one of the following: a mixture of epoxy monomers and thiol monomers, a mixture of epoxy monomers and amino monomers, a mixture of vinyl ether monomers and thiol monomers, a mixture of vinyl monomers and thiol monomers, or a mixture of monomers containing amino, hydroxyl, carboxyl, or thiol and isocyanate monomers. The positive-type liquid crystal, negative-type liquid crystal, and dual-frequency driven liquid crystal all include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, phase-transition liquid crystal having a smectic A phase-nematic phase, or phase-transition liquid crystal having a smectic A phase-cholesteric phase. The cholesteric liquid crystal is prepared using a cholesterol-based compound, a liquid crystal containing a cholesterol compound or a nematic liquid crystal, and a chiral compound. The smectic A phase-cholesteric phase having a phase transition liquid crystal is prepared using a cholesterol-based compound, a liquid crystal containing a cholesterol compound, or a phase transition liquid crystal having a smectic A phase-nematic phase and a chiral compound. The chiral molecule is S811, R811, S1011, R1011 or CB15. The initiator contains at least one of benzoin ethyl ether, benzophenone, thioxanthone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylacetone, trimethylbenzoyl, diphenylphosphine oxide, benzoin diethyl ether diazonium salt, diaryliodonium salt, triarylsulfonium salt, alkylsulfonium salt, iron aromatic hydrocarbon salt, sulfonyloxy ketone, triarylsiloxy ether, amine-based curing agent, dibutyltin, tributyltin or an organolead compound.

[0011] In some embodiments, the rod-shaped photopolymerizable monomer has a structure represented by any one of the following formulas (1) to (8), or is a plurality of compositions.

Chemical formula

[0012] In some embodiments, the raw material of the composite functional layer further contains a dye. The dye is an azo-based dye, an anthraquinone-based dye or a phthalocyanine-based dye.

[0013] In the second aspect of the present invention, a method for manufacturing the above liquid crystal film is provided. This method includes Step S1 of uniformly mixing all raw materials, adding them between substrates to fill the space between the substrates, and performing the first curing by ultraviolet irradiation polymerization and / or thermal polymerization to obtain Film A; Step S2 of performing the second curing by irradiating Film A with ultraviolet light through a photomask for t1 hours at temperature T1 under the condition that the liquid crystal material molecules in Film A are oriented or not oriented to obtain Film B; Step S3 of performing the third curing by irradiating Film B with ultraviolet light for t2 hours at temperature T2 under the condition that the liquid crystal material molecules in Film B are oriented or not oriented to obtain a liquid crystal film having an intelligent information encryption function; including.

[0014] In some embodiments, when the flexible polymerizable monomer is a flexible photopolymerizable monomer, the manufacturing method is as follows: Uniformly mixing all raw materials to form a precursor solution, adding the precursor solution between substrates to fill the space between the substrates to manufacture a film, and performing the first curing by irradiating the precursor solution with ultraviolet light through a photomask for t1 hours at temperature T1 under the condition of applying or not applying an electric field to the film to obtain Film A; Step of performing the second curing by irradiating Film A with ultraviolet light for t2 hours at temperature T2 under the condition that the liquid crystal material molecules in Film A are oriented or not oriented to obtain a liquid crystal film having an intelligent information encryption function; including.

[0015] In some embodiments, the orientation specifically controls the orientation of molecules by applying an electric field to Film A or Film B, and / or In S1, when the flexible polymerizable monomer is a flexible photopolymerizable monomer, ultraviolet irradiation polymerization is adopted, the temperature is -20 to 60 °C, the time is 5 to 90 s, and the intensity of ultraviolet light is 0.5 to 300 mW / cm 2If the flexible polymerizable monomer is a flexible thermal polymerizable monomer, thermal polymerization is employed, with a temperature of 20-120°C and a time of 0.1-1h; if the flexible polymerizable monomer is a mixture of a flexible photopolymerizable monomer and a flexible thermal polymerizable monomer, stepwise ultraviolet irradiation polymerization and thermal polymerization are performed on the flexible polymerizable monomer, and / or T1 is -20 to 60°C, t1 is 1 to 600 s, and UV intensity is 0.5 to 300 mW / cm². 2 and / or T2 is -20 to 60°C, t2 is 5 to 300 s, and UV intensity is 0.5 to 300 mW / cm². 2 That is the case.

[0016] A third aspect of the present invention relates to the use of the above-mentioned liquid crystal film or a liquid crystal film manufactured by the above-mentioned manufacturing method in a patternable and adjustable device.

[0017] Compared to the prior art, the present invention has the following beneficial effects. The liquid crystal film with intelligent information encryption function according to the present invention has different distribution densities of polymer networks in different regions and exhibits diverse responsiveness to electric fields, temperatures, magnetic fields, etc., enabling rich information pattern customization and realizing various visual effects such as changing information patterns from none to present, from present to none, and color changes, and also possesses an information encryption function.

[0018] In the manufacturing method of the present invention, by adjusting the polymerization rate, diffusion rate, and phase separation process, precise construction of a patterned network structure during the polymerization process is achieved, enabling the production of films with different patterned customizations, facilitating large-area processing, and offering a wide range of potential applications. [Brief explanation of the drawing]

[0019] To more clearly illustrate the technical means of the embodiments of the present invention, the drawings that need to be used in the description of the embodiments are briefly described below. Obviously, the drawings in the following description are only a few embodiments of the present invention, and those skilled in the art can obtain other drawings based on these without any creative effort.

[0020] [Figure 1] These are actual drawings of two types of masks used in embodiments of the present invention. [Figure 2] Figure 2a shows the manufacturing process and operating principle of the liquid crystal film of the present invention. Figure 2b shows the manufacturing process and operating principle of a liquid crystal film having the function of reversibly forming an information pattern by electrical control. [Figure 3] This is a drawing of a liquid crystal film having the function of reversibly encrypting information by electrical control according to Example 1. [Figure 4] This is a physical drawing of a liquid crystal film having the function of reversibly encrypting information by electrical control according to Examples 2 and 3. [Figure 5] This is a physical drawing of a liquid crystal film having the function of reversibly encrypting information by temperature control according to Example 4. [Figure 6] This is a physical drawing of a liquid crystal film having the function of reversibly encrypting information by temperature control according to Example 5. [Figure 7] This is a physical drawing of a liquid crystal film having the function of reversibly encrypting information by electrical control according to Example 7. [Modes for carrying out the invention]

[0021] The technical concepts in embodiments of the present invention will be described clearly and completely below with reference to the drawings of the embodiments. Clearly, the embodiments described are only some, not all, embodiments of the present invention. All other embodiments obtained by those skilled in the art without creative work based on embodiments of the present invention are within the scope of the protection of the present invention.

[0022] In the following description of this embodiment, the terms "include," "contain," "have," and "contain" are all open terms, meaning that "include" does not mean "not limited to" these terms.

[0023] In the following description of this embodiment, the terms "and / or" are used to describe the relationship between related objects and indicate three types of relationships. For example, A and / or B indicates that A exists alone, B exists alone, and A and B exist simultaneously. However, A and B may be singular or plural. The letter " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0024] In the following description of this embodiment, the term "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions means any combination of these items, including a single item or any combination of multiple items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can represent a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c may each be one or more.

[0025] The terms used in the embodiments of the present invention are for the purpose of describing specific embodiments and are not intended to limit the invention. The singular forms “one” and “the said” used in the embodiments of the present invention and in the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0026] Those skilled in the art will understand that in the following description of embodiments of the present invention, the order of sequence numbers does not imply the order of execution, some or all of the steps may be executed in parallel or one after the other, and the execution order of each process should be determined by its function and internal logic, and is not intended to limit the implementation of embodiments of the present invention.

[0027] Those skilled in the art will understand that the numerical ranges in the embodiments of the present invention specifically disclose the intermediate values ​​between the upper and lower limits of the range. Any descriptive value or intermediate value within the descriptive range, and any smaller range between any other descriptive value or intermediate value within the said range, are also included in the present invention. The upper and lower limits of these ranges may or may not be included within the range, independently of each other.

[0028] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as those generally understood by those skilled in the art. While this invention describes only preferred methods and materials, any similar or equivalent methods and materials may be used in the implementation or testing of this invention. All references mentioned herein are incorporated by reference to disclose and describe methods and / or materials related to those references. In the event of any conflict with any incorporated reference, the provisions of this specification shall prevail.

[0029] In a first aspect of the present invention, a liquid crystal film having an intelligent information encryption function is provided, comprising two parallel transparent substrates and a composite functional layer located between the transparent substrates, wherein the composite functional layer comprises a honeycomb polymer matrix and a liquid crystal mixture filling the pores of the polymer matrix, the liquid crystal mixture having a polymer network, and the distribution density of the polymer network differs in different regions of the liquid crystal film, thereby providing a liquid crystal film having an information pattern that reversibly changes so as to disappear (or appear) when an electric field is applied and reappear (or disappear) after the electric field is cut off, or an information pattern that reversibly changes so as to disappear (or appear) at low temperatures and reappear (or disappear) at high temperatures.

[0030] Specifically, based on differences in the orientation of liquid crystal molecules in different regions, or the same orientation of liquid crystal molecules but different anchoring forces of the polymer network on the liquid crystal molecules, the liquid crystal film, under the influence of an external field (e.g., electric field, magnetic field, or temperature), exhibits or disappears information patterns due to differences in the degree of change in light transmittance or light scattering intensity in those different regions, and after the external field is removed, the liquid crystal film returns to its initial state.

[0031] In the present invention, a liquid crystal film having an intelligent information encryption function refers to a film material that can reversibly switch a predetermined information pattern between a visible state and an invisible state by applying an electric field or changing the temperature, thereby realizing an information encryption and display function that dynamically hides and reveals information.

[0032] In the present invention, the transparent substrate is a glass substrate, a PET substrate, or a glass / PET substrate having a transparent indium tin oxide (ITO) conductive coating.

[0033] In the present invention, the composite functional layer between the two substrates has a polymer matrix that exhibits a honeycomb-like porous structure, and liquid crystal is filled into the pores of the polymer matrix. The liquid crystal has a polymer network. The polymer network fibers can exhibit a non-oriented or oriented arrangement, for example, a vertical, parallel, or helical arrangement. The polymer network has different densities in different regions of the liquid crystal film.

[0034] The liquid crystal film of the present invention can exhibit a pattern change process from nothing to something or from something to nothing under the action of an electric field. For example, if a positive-type cholesteric liquid crystal is selected and the polymer network is vertically oriented, the liquid crystal film exhibits a transparent or translucent state in regions with high polymer fiber density, where the liquid crystal molecules are restricted by the orientation-regulating force (anchoring effect) of the polymer network. In regions with low polymer fiber density, the liquid crystal film exhibits a focal conic molecular orientation under the action of the polymer network, resulting in a light-scattering state. If the region of light scattering in the liquid crystal film is small and the transparent or translucent region is large, a light-scattering pattern appears in the background of the transparent or translucent area. When an electric current is applied to the liquid crystal film, the liquid crystal in the region with low polymer fiber density becomes vertically oriented and transparent, the light-scattering region disappears, the entire film becomes transparent, and the information pattern disappears. When the power supply is cut off, liquid crystal molecules in regions with low polymer fiber density enter a focal conic molecular orientation, exhibiting a light scattering state, and a new information pattern emerges. This enables the liquid crystal film to achieve a reversible information patterning function.

[0035] For example, if the liquid crystal is a negative-type liquid crystal or a dual-frequency driven liquid crystal, the liquid crystal film can realize a reversible information patterning function in which a pattern appears when an electric field is applied and disappears after the electric field is cut off.

[0036] In this invention, when the liquid crystal is a smectic A-cholesteric phase transition liquid crystal (SmA-LC) and the polymer network is vertically oriented, the liquid crystal film exhibits a pattern change process from nothing to present with respect to temperature changes. For example, when a liquid crystal is selected in which the polymer network is vertically oriented, exhibits the smectic A phase at low temperatures, and exhibits the cholesteric phase at high temperatures, at low temperatures the smectic A liquid crystal molecules are vertically oriented, and the liquid crystal film is transparent. When the liquid crystal film is heated to the cholesteric phase, in regions with high polymer fiber density, the liquid crystal molecules are restricted by the orientation-restricting force of the polymer network, and the liquid crystal molecules remain vertically oriented, and the film is transparent in this region. However, in regions with low polymer fiber density, the orientation-restricting force of the polymer network on the liquid crystal molecules is weak, and the cholesteric liquid crystal molecules enter a focal conic molecular orientation, in which case the film enters a light-scattering state in this region. Depending on the mask size, as the temperature increases, it is possible to display a light-scattering pattern on a transparent background, or a transparent information pattern on a light-scattering background, thereby realizing a change from nothing to present in the information pattern. As the temperature decreases, the information pattern disappears. Therefore, with temperature changes, the film exhibits a reversible change in the information pattern, from nothing to something.

[0037] When using a liquid crystal having a smectic A-cholesteric phase transition, the polymer network in some areas of the film is vertically oriented and has a low fiber density. This part of the film is transparent at low temperatures and exhibits a light-scattering state at high temperatures. In other areas of the film, the polymer network exhibits a random orientation (unoriented). The liquid crystal in this part has a focal conic molecular orientation and is regulated by the polymer network. The film exhibits a light-scattering state at high temperatures. Depending on the size of the mask, it is possible to display a light-scattering information pattern on a transparent background or a transparent information pattern on a light-scattering background. As the temperature increases, the transparent areas become light-scattering, the pattern disappears, and the information pattern changes from present to absent.

[0038] In a preferred embodiment of the present invention, the composite functional layer further comprises a dye such as an azo dye, an anthraquinone dye, or a phthalocyanine dye. In this case, the liquid crystal film can exhibit different colors. Depending on whether the power is turned on or off or the temperature is high or low, the color in each region of the liquid crystal film changes, providing the liquid crystal film with a reversible color patterning function.

[0039] In the present invention, the raw materials for the composite functional layer include, by weight %, 5 wt% to 60 wt% of a flexible polymerizable monomer, 0.5 wt% to 15 wt% of a rod-shaped photopolymerizable monomer, 20 wt% to 94.4 wt% of a liquid crystal, 0.1 wt% to 5 wt% of an initiator, and spacer particles in an amount of 0.1 wt% to 2 wt% of the sum of the amounts of the flexible polymerizable monomer, rod-shaped photopolymerizable monomer, liquid crystal mixture, and initiator. In the present invention, the spacer particles are preferably polystyrene microspheres.

[0040] In the present invention, the flexible polymerizable monomer comprises at least one of a flexible photopolymerizable monomer or a flexible thermal polymerizable monomer. The flexible photopolymerizable monomer undergoes radical polymerization or cationic polymerization under ultraviolet irradiation and comprises at least one of an acrylate monomer, an olefin monomer, a vinyl ether monomer, or an epoxy monomer. The flexible thermal polymerizable monomer can be thermally polymerized under heating conditions and comprises at least one of a mixture of an epoxy monomer and a thiol monomer, a mixture of an epoxy monomer and an amino monomer, a mixture of a vinyl ether monomer and a thiol monomer, a mixture of a vinyl monomer and a thiol monomer, or a mixture of a monomer containing amino, hydroxyl, carboxyl, or thiol and an isocyanate monomer.

[0041] The flexible polymerizable monomer is preferably hydroxypropyl methacrylate (HPMA), lauryl methacrylate (LMA), polyethylene glycol diacrylate (PEGDA600), or bisphenol A ethoxylate dimethacrylate (Bis-EMA15), and more preferably a mixture of the four monomers HPMA, LMA, PEGDA600, and Bis-EMA15. The chemical formulas of the above four monomers are as follows. [ka]

[0042] In the present invention, depending on the performance requirements of the final device, the liquid crystal can be a positive-type liquid crystal, a negative-type liquid crystal, or a dual-frequency driven liquid crystal. The positive-type liquid crystal, negative-type liquid crystal, or dual-frequency driven liquid crystal can be a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a liquid crystal having a smectic-A-nematic phase transition, or a liquid crystal having a smectic-A-cholesteric phase transition, for example, a positive-type nematic liquid crystal or a negative-type cholesteric liquid crystal. The cholesteric liquid crystal of the present invention can be manufactured using a cholesterol-based compound, a liquid crystal containing a cholesterol compound, or a nematic liquid crystal and a chiral compound. The liquid crystal having a smectic-A-cholesteric phase transition can be manufactured using a cholesterol-based compound, a liquid crystal containing a cholesterol compound, or a liquid crystal having a smectic-A-nematic phase transition and a chiral compound.

[0043] Specifically, the chiral molecule can be a chiral compound of products such as S811, R811, S1011, R1011, or CB15, and the amount used is 0.1 to 90 wt%, preferably 0.1 to 4 wt%, of the mass of the cholesteric liquid crystal or liquid crystal having a smectic A-cholesteric phase transition. In the present invention, the chiral compound is preferably S811 or CB15. The chemical formula for S811 is as follows. [ka]

[0044] The rod-shaped photopolymerizable monomer has a rigid structure and can undergo radical polymerization or cationic polymerization under ultraviolet irradiation, or can undergo both radical polymerization and cationic polymerization under ultraviolet irradiation. Preferably, it contains one or more of the structures represented by the following formulas (1) to (8). [ka] Here, m is between 1 and 20, n is between 1 and 20, x is between 1 and 2, and y is between 1 and 2. E and Q are acrylate, epoxy, vinyl ether, or olefin functional groups.

[0045] In the present invention, the rod-shaped photopolymerizable monomer is preferably C6M, and its chemical formula is as follows. [ka]

[0046] In the present invention, radical initiators, cationic photoinitiators, or thermal initiators can be used as the initiator. Radical initiators include at least one of benzoin ethyl ether, benzophenone, thioxanthone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylacetone, trimethylbenzoyl, diphenylphosphine oxide, or benzoin diethyl ether. Cationic photoinitiators include at least one of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron aromatic hydrocarbon salts, sulfonyloxyketones, or triarylsiloxy ethers. Thermal initiators include at least one of amine-based curing agents, dibutyltin, tributyltin, or organolead compounds. The amine-based curing agent is preferably K-54 or DMP-30.

[0047] In the embodiments of the present invention, the photoinitiator is preferably benzyldimethyl ketal, i.e., photoinitiator 651, and its chemical formula is as follows. [ka]

[0048] In the present invention, the spacer particles are preferably polystyrene microspheres.

[0049] In a second aspect, the present invention provides a method for manufacturing a liquid crystal film having an intelligent information encryption function. This method includes the following steps S1 to S3.

[0050] S1: The raw materials are uniformly mixed and added to the spaces between the substrates until the spaces between the substrates are filled. The first curing is performed by ultraviolet irradiation polymerization and / or thermal polymerization to obtain film A.

[0051] Specifically, under ultraviolet irradiation and the action of a photoinitiator, the flexible photopolymerizable monomer polymerizes and hardens upon ultraviolet irradiation, forming a honeycomb-like polymer matrix that fills the pores of the polymer matrix with liquid crystal. A small amount of the rod-shaped photopolymerizable monomer polymerizes and hardens, with most of it distributed within the liquid crystal. This is because the collision probability between radicals of the flexible polymerizable monomer is much higher than that between radicals of the rigid rod-shaped photopolymerizable monomer, so during the first photocuring, the flexible photopolymerizable monomer hardens mainly within a certain time.

[0052] When a flexible thermopolymerizable monomer is used as the flexible polymerizable monomer, under heating conditions, the flexible thermopolymerizable monomer undergoes thermal polymerization and hardens, forming a honeycomb-like polymer matrix, and liquid crystals fill the pores of the polymer matrix. Rod-shaped photopolymerizable monomers are distributed in the liquid crystal without polymerization and hardening.

[0053] When the flexible polymerizable monomer is a flexible photopolymerizable monomer, the UV irradiation polymerization temperature is -20 to 60°C, the time is 5 to 90 seconds, and the UV intensity is 0.5 to 300 mW / cm². 2 When a flexible polymerizable monomer is a flexible thermopolymerizable monomer, the thermal polymerization temperature is 20-120°C and the time is 0.1-1h.

[0054] When the flexible polymerizable monomer is a mixture of a flexible photopolymerizable monomer and a flexible thermopolymerizable monomer, the flexible polymerizable monomer can be cured by stepwise ultraviolet irradiation polymerization and thermal polymerization.

[0055] S2: The liquid crystal molecules in film A are oriented or unoriented, and film A is cured a second time by irradiating it with ultraviolet light at a temperature T1 through a mask for t1 hours to obtain film B.

[0056] Specifically, by applying an electric field to film A to control the orientation of liquid crystal molecules, the rod-shaped photopolymerizable monomers can be oriented and arranged along the direction of the electric field together with the liquid crystal molecules, or they can be oriented and arranged together with the liquid crystal molecules in response to temperature changes. When it is necessary to orient film A, a mask is placed over film A at temperature T1, an electric field is applied to orient the rod-shaped photopolymerizable monomers and liquid crystal molecules in film A, and film A is irradiated with ultraviolet light through the mask to polymerize the photopolymerizable monomers in the light-transmitting region of the mask, thereby performing a second curing. The mask of the present invention is shown in Figure 1.

[0057] During the second curing cycle, T1 is -20 to 60°C. Depending on the specific requirements of the customized pattern, T1 can be 1 to 600 seconds, and the UV intensity can be 0.5 to 300 mW / cm². 2 That is the case.

[0058] S3: By applying an electric field to film B, orientation or non-orientation is achieved, and a third curing is performed by irradiating film B with ultraviolet light at a temperature T2 for t2 hours to obtain a liquid crystal film with intelligent information encryption functionality.

[0059] By applying an electric field to film B to control the orientation of molecules, the rod-shaped photopolymerizable monomers can be aligned along the direction of the electric field together with the liquid crystal molecules, or aligned together with the liquid crystal molecules in response to temperature changes. If it is necessary to orient film B, an electric field is applied to film B at temperature T2 to orient the unpolymerized rod-shaped photopolymerizable monomers and liquid crystal molecules, and by irradiating film B with ultraviolet light, the rod-shaped photopolymerizable monomers in the area shielded by the mask undergo polymerization during the second curing process, followed by a third curing. Here, T2 is -20 to 60°C. Depending on the specific requirements of the customized pattern, t2 is 5 to 300 s, and the ultraviolet intensity is 0.5 to 500 mW / cm². 2 That is the case.

[0060] After the second photocuring, the curing temperature of the rod-shaped photopolymerizable monomer differs between the area not shielded by the mask and the area shielded by the mask, or the content of the remaining rod-shaped photopolymerizable monomer differs. After the third photocuring, the density of the polymer network differs between the area not shielded by the mask and the area shielded by the mask during the second curing process. In this invention, the second and third curing processes result in the formation of polymer networks with a certain orientation and different fiber densities in the light-transmitting area not shielded by the mask and the shielded area of ​​the liquid crystal film.

[0061] In the present invention, when using a liquid crystal material having a specific phase transition, the desired film can be manufactured by the above manufacturing method, and it is not necessary to apply an electric field. By adjusting the second curing temperature T1 and the third curing temperature T2, the molecular orientation of the liquid crystal and photopolymerizable monomer mixture during the second and third photocuring processes of the rod-shaped photopolymerizable monomer is controlled, thereby controlling the orientation of the formed polymer network fibers. Furthermore, the radicals of the rod-shaped photopolymerizable monomer have different diffusion rates at high and low temperatures and in different phase states, and the polymer network fibers have different densities in different regions depending on the use of the mask.

[0062] In the liquid crystal film of the present invention, the orientation of the polymer network may be the same or different in regions where the fiber density of the polymer network is different.

[0063] In the present invention, when the flexible photopolymerizable monomer is a flexible photopolymerizable monomer, the radical collision probability of the flexible photopolymerizable monomer is higher than that of the rod-shaped photopolymerizable monomer, and when both are present, the polymerization rate of the flexible photopolymerizable monomer is faster than that of the rod-shaped photopolymerizable monomer. Therefore, steps S1 and S2 in the described manufacturing method can be combined into a single step. It may also be manufactured by the following method. Each raw material is uniformly mixed to form a precursor solution, and the precursor solution is added between the substrates until the spaces between the substrates are filled to manufacture a film. The first curing is performed by irradiating the precursor solution with ultraviolet light for t1 hours at a temperature T1, either by applying an electric field to the film or not applying an electric field, to obtain film A. A liquid crystal film with intelligent information encryption functionality is obtained by performing a second curing process by irradiating film A with ultraviolet light for t2 hours at a temperature T2, under conditions where the liquid crystal material molecules in film A are oriented or unoriented.

[0064] In this case, T1 is -20 to 60°C, T2 is -20 to 60°C, t1 is 1 to 600 s, t2 is 5 to 300 s, and the UV intensity is 0.5 to 300 mW / cm². 2 That is the case.

[0065] Figure 2 shows the manufacturing process and operating principle of the liquid crystal film according to the present invention. When the liquid crystal used is a positive-type cholesteric liquid crystal, this liquid crystal film is a liquid crystal film that has the function of reversibly forming an information pattern by electrical control. Its manufacturing process and operating principle are shown in Figure 2a. When no electric field is applied, in regions where the fiber density of the polymer network is low, the anchoring effect (orientation restricting effect) of the polymer network on the liquid crystal is relatively small, the liquid crystal molecules form a random orientation, and the liquid crystal film becomes a scattering state. In regions where the fiber density of the polymer network is high, the anchoring effect of the polymer network on the liquid crystal molecules is relatively large, the liquid crystal molecules are vertically oriented, and the liquid crystal film becomes transparent. In this case, a light scattering pattern appears on a transparent background (Figure 3). By controlling the size of the mask, a transparent pattern can also appear on a light scattering background (Figure 4). After the application of an electric field, the liquid crystal is vertically oriented, the entire liquid crystal film changes to a transparent state, and the pattern disappears. After the electric field is cut off, the pattern reappears.

[0066] The present invention relates to a liquid crystal film in which, when the liquid crystal used is a liquid crystal material having a certain phase transition, for example, a liquid crystal material having a smectic A-cholesteric phase transition, and the polymer network is vertically oriented, this liquid crystal film has the function of reversibly forming an information pattern by temperature control. Its manufacturing process and operating principle are shown in Figure 2b. When the ambient temperature is lower than the phase transition temperature of the liquid crystal, the smectic A liquid crystal molecules are vertically oriented, and the entire film is transparent. When the ambient temperature is higher than the phase transition temperature of the liquid crystal, in regions of the liquid crystal film with a low polymer network fiber density, the anchoring effect of the polymer network on the liquid crystal is small, the liquid crystal undergoes a phase transition, and the film enters a scattering state. In regions of the liquid crystal film with a high polymer network fiber density, the anchoring effect of the polymer network on the liquid crystal molecules is large, and when the liquid crystal is heated and enters the cholesteric phase, the liquid crystal molecules are still vertically oriented, and the film remains transparent. In this case, a predetermined light scattering pattern appears on a transparent background (Figure 5). By controlling the size of the mask, a transparent pattern appears on the background of the light scattering (Figure 6). If the ambient temperature is lower than the phase transition temperature, the entire film becomes transparent and the pattern disappears.

[0067] The liquid crystal film of the present invention has an intelligent information encryption function and can be applied to devices with controllable information patterns. On the liquid crystal film, an information pattern is displayed (or not displayed) before an electric field is applied, the information pattern disappears (or reappears) after an electric field is applied, and the information pattern reappears (or not reappears) after the electric field is turned off. Alternatively, if the liquid crystal film is below the liquid crystal phase transition temperature, there is no information pattern (or there is an information pattern), if it is above the liquid crystal phase transition temperature, the information pattern is displayed (or not displayed), and if the ambient temperature is below the liquid crystal phase transition temperature, the information pattern disappears (or reappears) again. By designing the shape and size of the mask, regions of different shapes and sizes with different light transmittances can be manufactured, thereby enabling the customization of specific information patterns on the liquid crystal film, and a wide range of applications are expected in the fields of electronic consumption and information encryption.

[0068] The present invention will be further described by way of examples below.

[0069] Example 1 According to this example, a method for manufacturing a liquid crystal film having a function of reversibly forming an information pattern by electrical control is provided. The raw materials and their mixing ratios are shown in Table 1.

[0070] Table 1: Raw material mixing ratio of Example 1 [Table 1] Here, the nematic liquid crystal SLC-1717 and the chiral compound S811 are commercially available products of Shijiazhuang Chengzhi Zhiyonghua Display Materials Co., Ltd.

[0071] S1: The raw materials listed in Table 1 were uniformly mixed and interposed between two layers of ITO conductive plastic films. Ultraviolet light with a light intensity of 10 mW / cm 2 was irradiated on the film for 20 s at 15 °C to initiate the polymerization of most of the flexible photopolymerizable monomers, and a film A having a honeycomb-like polymer matrix was obtained. S2: A customized mask was placed on the upper surface of film A, and an electric field was applied to film A to convert the film into a transparent state. Film A was heated to 40 °C, and ultraviolet light with a light intensity of 15 mW / cm 2 was irradiated on film A for 600 s to form a region with a high fiber density of the polymer network in the light transmission region of the mask, and film B was obtained. S3: The mask was removed, and an electric field was continuously applied to keep film B in a transparent state. Ultraviolet light with a light intensity of 5 mW / cm 2 was irradiated on the film for 180 s at 15 °C. A region with a low fiber density of the polymer network was formed in the region other than the region with a high fiber density of the polymer network formed in step S2, and a liquid crystal film having an intelligent information encryption function was obtained.

[0072] The mask used in Example 1 is the mask shown on the right side of Figure 1, and Figure 3 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. When no electric field is applied, the Huawei logo appears on a transparent background due to light scattering. After applying an electric field, the entire film becomes transparent and the information pattern disappears.

[0073] Example 2 In this embodiment, a method for manufacturing a liquid crystal film having the function of reversibly forming an information pattern by electrical control is provided. The raw materials and their mixing ratios are shown in Table 1. S1: The raw materials listed in Table 1 were uniformly mixed and interposed between two layers of ITO conductive plastic film. Under conditions of 15°C, the light intensity was 10 mW / cm². 2 The film was irradiated with ultraviolet light for 20 seconds to initiate polymerization of most of the flexible photopolymerizable monomers, obtaining film A having a honeycomb polymer matrix. S2: A customized mask was placed on top of film A, and an electric field was applied to film A to convert the film to a transparent state. Film A was heated to 40°C, and the light intensity was 15 mW / cm². 2 By irradiating film A with ultraviolet light for 600 s, a region with a high fiber density of the polymer network was formed in the light-transmitting area of ​​the mask, thereby obtaining film B. S3: The mask was removed and the electric field was continued to be applied. Film B was kept transparent, and the light intensity was 5 mW / cm² at 15°C. 2 The film was irradiated with ultraviolet light for 180 seconds. Regions with a low fiber density of the polymer network were formed in areas other than the region with a high fiber density of the polymer network formed in step S2, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0074] The mask used in Example 2 is the mask shown on the left side of Figure 1, and Figure 4 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. When no electric field is applied, a transparent Huawei logo appears in the background of the light scattering state. After applying an electric field, the entire film becomes transparent and the information pattern disappears.

[0075] Example 3 In this embodiment, a method for manufacturing a liquid crystal film having the function of reversibly forming an information pattern by electrical control is provided. The raw materials and their mixing ratios are shown in Table 1. S1: The raw materials listed in Table 1 were uniformly mixed and interposed between two layers of ITO conductive plastic film. Under conditions of 15°C, the light intensity was 10 mW / cm². 2 The film was irradiated with ultraviolet light for 20 seconds to initiate polymerization of most of the flexible photopolymerizable monomers, obtaining film A having a honeycomb polymer matrix. S2: A customized mask was placed on top of film A, and an electric field was applied to film A to convert the film to a transparent state. Film A was heated to 15°C, and the light intensity was 5 mW / cm². 2 Ultraviolet light was irradiated onto film A for 180 seconds to form a region with a low fiber density in the polymer network within the light-transmitting area of ​​the mask, thereby obtaining film B. S3: The mask was removed and the electric field was continued to be applied. Film B was kept transparent, and the light intensity was 15 mW / cm² at 40°C. 2 By irradiating the film with ultraviolet light for 600 seconds, regions with a high fiber density of the polymer network were formed in areas other than those with a low fiber density in the polymer network formed in step S2, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0076] The mask used in Example 3 is the mask shown on the right side of Figure 1, and Figure 4 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. When no electric field is applied, a transparent Huawei logo appears in the background of the light scattering state. After applying an electric field, the entire film becomes transparent and the information pattern disappears.

[0077] Example 4 This embodiment provides a method for manufacturing a liquid crystal film that has the function of reversibly forming a pattern by temperature control. The raw materials and their mixing ratios are shown in Table 2.

[0078] Table 2: Raw material blending ratio of Example 4 [Table 2] Here, the liquid crystal with a smectic-cholesteric phase transition (SmA-ChLC) is the liquid crystal material product SZYH-08A from Beijing Suzhou Yinghui Iris Thin Film Materials Technology Co., Ltd.

[0079] S1: The raw materials listed in Table 2 were uniformly mixed and interposed between two layers of ITO conductive plastic film. Under conditions of 15°C, the light intensity was 10 mW / cm². 2 The film was irradiated with ultraviolet light for 20 seconds to initiate polymerization of most of the flexible photopolymerizable monomers, obtaining film A having a honeycomb polymer matrix. S2: A customized mask was placed on top of film A, and an electric field was applied to film A to convert the film to a transparent state. Film A was heated to 40°C, and the light intensity was 15 mW / cm². 2 Ultraviolet light was irradiated onto film A for 600 seconds, forming a region with a high fiber density of the polymer network in the light-transmitting area of ​​the mask, thereby obtaining film B. S3: The mask was removed and the electric field was continued to be applied. Film B was kept transparent, and the light intensity was 5 mW / cm² at 15°C. 2 By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density in the polymer network formed in step S2, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0080] The mask used in Example 4 is the mask shown on the right side of Figure 1, and Figure 5 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. At low temperatures, the liquid crystal film is transparent, and at high temperatures, a Huawei logo pattern in a light-scattering state appears on the transparent background.

[0081] Example 5 In this embodiment, a method for manufacturing a liquid crystal film having the function of reversibly forming a pattern by temperature control is provided. The raw materials and their mixing ratios are shown in Table 2. The manufacturing steps are as follows. S1: The raw materials listed in Table 2 were uniformly mixed and interposed between two layers of ITO conductive plastic film. Under conditions of 15°C, the light intensity was 10 mW / cm². 2 The film was irradiated with ultraviolet light for 20 seconds to initiate polymerization of most of the flexible photopolymerizable monomers, obtaining film A having a honeycomb polymer matrix. S2: A customized mask was placed on top of film A, and an electric field was applied to film A to convert the film to a transparent state. Film A was heated to 40°C, and the light intensity was 15 mW / cm². 2 By irradiating film A with ultraviolet light for 600 s, a region with a high fiber density of the polymer network was formed in the light-transmitting area of ​​the mask, thereby obtaining film B. S3: The mask was removed and the electric field was continued to be applied. Film B was kept transparent, and the light intensity was 5 mW / cm² at 15°C. 2 By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density in the polymer network formed in step S2, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0082] The mask used in Example 5 is the mask shown on the left side of Figure 1, and Figure 6 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. At low temperatures, the liquid crystal film is transparent, and at high temperatures, a transparent Huawei logo pattern appears in the background of the light scattering state.

[0083] Example 6 In this embodiment, a method for manufacturing a liquid crystal film having the function of reversibly forming a pattern by temperature control is provided. The raw materials and their mixing ratios are shown in Table 2. The manufacturing steps are as follows. S1: The raw materials listed in Table 2 were uniformly mixed and interposed between two layers of ITO conductive plastic film. Under conditions of 15°C, the light intensity was 10 mW / cm². 2 The film was irradiated with ultraviolet light for 20 seconds to initiate polymerization of most of the flexible photopolymerizable monomers, obtaining film A having a honeycomb polymer matrix. S2: A customized mask was placed on top of film A, and film A was heated to 40°C. The light intensity was 15 mW / cm². 2 By irradiating film A with ultraviolet light for 600 s, a region with a high fiber density of the polymer network was formed in the light-transmitting area of ​​the mask, resulting in film B exhibiting light scattering. S3: The mask was removed, and an electric field was applied to the film, which kept the film transparent in areas other than those with a high fiber density in the formed polymer network. The light intensity was 5 mW / cm² at 15°C. 2 By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0084] The mask used in Example 6 is the mask shown on the left or right side of Figure 1. This film displays a transparent pattern on a light-scattering background at low temperatures, or a light-scattering pattern on a transparent background. At high temperatures, the pattern disappears, and the entire film becomes light-scattering.

[0085] Example 7 In this embodiment, a two-step manufacturing method for a liquid crystal film having an electrically controlled reversible patterning function is provided. The raw materials and their mixing ratios are shown in Table 1. The manufacturing steps are as follows. S1: The raw materials listed in Table 1 were uniformly mixed and interposed between two layers of ITO conductive plastic film. An electric field was applied to the film, and a customized mask was placed on the ITO conductive plastic film. The light intensity was 20 mW / cm² under conditions of 50°C. 2 By irradiating the film with ultraviolet light for 600 seconds, a region with a high fiber density of the polymer network was formed in the light-transmitting area of ​​the mask, thereby obtaining film A. S2: Remove the mask, continue applying the electric field, keep film A transparent, and the light intensity is 5 mW / cm² at 15°C. 2By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density in the polymer network formed in step S1, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0086] The mask used in Example 7 is the mask shown on the right side of Figure 1, and Figure 7 shows a physical representation of the manufactured liquid crystal film with intelligent information encryption capabilities. When no electric field is applied, the Huawei logo appears as light scattering on a transparent background. After applying an electric field, the entire film becomes transparent and the information pattern disappears.

[0087] Example 8 In this embodiment, a two-step manufacturing method for a liquid crystal film having the function of reversibly forming a pattern by temperature control is provided. The raw materials and their mixing ratios are shown in Table 2. The manufacturing steps are as follows. S1: The raw materials listed in Table 2 were uniformly mixed and interposed between two layers of ITO conductive plastic film. An electric field was applied to the film, and a customized mask was placed on the ITO conductive plastic film. The light intensity was 20 mW / cm² under conditions of 50°C. 2 The film was irradiated with ultraviolet light for 600 seconds, forming a region with a high fiber density of the polymer network in the light-transmitting area of ​​the mask, thereby obtaining film A. S2: Remove the mask, continue applying the electric field, keep film A transparent, and under conditions of 15°C, the light intensity is 5 mW / cm². 2 By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density in the polymer network formed in step S1, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0088] The mask used in Example 8 is the mask shown on the left or right side of Figure 1, and a liquid crystal film with intelligent information encryption functionality was manufactured. At low temperatures, the film was transparent, and at high temperatures, a light scattering pattern appeared on a transparent background, or a transparent pattern appeared on a light scattering background.

[0089] Example 9 In this embodiment, a two-step manufacturing method for a liquid crystal film having the function of reversibly forming a pattern by temperature control is provided. The raw materials and their mixing ratios are shown in Table 2. The manufacturing steps are as follows. S1: The raw materials listed in Table 2 were uniformly mixed and interposed between two layers of ITO conductive plastic film. A customized mask was placed on the ITO conductive plastic film. Light intensity was 20 mW / cm² at 50°C. 2 The film was irradiated with ultraviolet light for 600 seconds, forming a region with a high fiber density of the polymer network in the light-transmitting area of ​​the mask, thereby obtaining film A. S2: The mask was removed, and the electric field was continued to be applied, keeping the areas of film A transparent except for those with high fiber density in the polymer network. The light intensity was 5 mW / cm² at 15°C. 2 By irradiating the film with ultraviolet light for 180 seconds, regions with a low fiber density of the polymer network were formed in areas other than those with a high fiber density, thereby obtaining a liquid crystal film with intelligent information encryption capabilities.

[0090] The mask used in Example 9 is the mask shown on the left or right side of Figure 1, and a liquid crystal film with intelligent information encryption functionality was manufactured. At low temperatures, the film showed either a light scattering pattern on a transparent background or a transparent pattern on a light scattering background. At high temperatures, the pattern disappeared, and the entire film entered a light scattering state.

[0091] While the present invention has been described in detail in this specification using general descriptions and specific embodiments, several modifications or improvements to the present invention will be apparent to those skilled in the art. Therefore, any such modifications or improvements made without departing from the spirit of the invention will fall within the scope of protection of the present invention.

Claims

1. A liquid crystal film having an intelligent information encryption function, A liquid crystal film comprising two parallel transparent substrates and a composite functional layer located between the transparent substrates, wherein the composite functional layer comprises a honeycomb polymer matrix and liquid crystals filling the pores of the polymer matrix, the liquid crystal having a polymer network, and the distribution density of the polymer network differs in different regions of the liquid crystal film, so that the liquid crystal film has an information pattern that reversibly changes so as to disappear (or appear) when an electric field is applied and reappear (or disappear) after the electric field is cut off, or an information pattern that reversibly changes so as to disappear (or appear) at low temperatures and reappear (or disappear) at high temperatures.

2. The raw materials for the composite functional layer are by weight % Flexible polymerizable monomer in an amount of 5 wt% to 60 wt%, 0.5 wt% to 15 wt% of rod-shaped photopolymerizable monomer, LCD 20 wt% to 94.4 wt%, Initiator 0.1 wt% to 5 wt%, Spacer particles in a dose of 0.1 wt% to 2 wt% of the sum of the doses of the flexible polymerizable monomer, rod-shaped photopolymerizable monomer, liquid crystal mixture, and initiator, A liquid crystal film according to claim 1, characterized by including the following:

3. The flexible polymerizable monomer comprises at least one of a flexible photopolymerizable monomer or a flexible thermal polymerizable monomer, wherein the flexible photopolymerizable monomer is subjected to radical polymerization or cationic polymerization under ultraviolet irradiation, and the flexible thermal polymerizable monomer is subjected to thermal polymerization under heating conditions. The rod-shaped photopolymerizable monomer is subjected to radical polymerization or cationic polymerization under ultraviolet irradiation. The liquid crystal is a positive-type liquid crystal, a negative-type liquid crystal, or a dual-frequency driven liquid crystal. The initiator is a radical initiator, a cationic photoinitiator, or a thermal initiator. The liquid crystal film according to claim 2, characterized in that the spacer particles are microspheres of styrene or silicon dioxide, and have a diameter of 2 μm to 100 μm.

4. The flexible photopolymerizable monomer comprises at least one of acrylate monomers, olefin monomers, vinyl ether monomers, or epoxy monomers. The flexible, thermopolymerizable monomer comprises at least one of the following: a mixture of epoxy monomers and thiol monomers, a mixture of epoxy monomers and amino monomers, a mixture of vinyl ether monomers and thiol monomers, a mixture of vinyl monomers and thiol monomers, or a mixture of monomers containing amino, hydroxyl, carboxyl, or thiol and isocyanate monomers. The positive-type liquid crystal, negative-type liquid crystal, and dual-frequency driven liquid crystal all include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, phase-transition liquid crystal having a smectic A phase-nematic phase, or phase-transition liquid crystal having a smectic A phase-cholesteric phase. The cholesteric liquid crystal is prepared using a cholesterol-based compound, a liquid crystal or nematic liquid crystal containing a cholesterol-based compound, and a chiral compound; the phase transition liquid crystal having a smectic A phase-cholesteric phase is prepared using a cholesterol-based compound, a liquid crystal containing a cholesterol-based compound, or a phase transition liquid crystal having a smectic A phase-nematic phase, and a chiral compound; and the chiral molecule is S811, R811, S1011, R1011, or CB15. The liquid crystal film according to claim 3, characterized in that the initiator comprises at least one of the following: benzoin ethyl ether, benzophenone, thioxanthone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylacetone, trimethylbenzoyl, diphenylphosphine oxide, benzoin diethyl ether diazonium salt, diaryliodonium salt, triarylsulfonium salt, alkylsulfonium salt, iron aromatic hydrocarbon salt, sulfonyloxyketone, triarylsiloxy ether, amine-based curing agent, dibutyltin, tributyltin, or organolead compound.

5. The rod-shaped photopolymerizable monomer has a structure represented by any one of the following formulas (1) to (8), or is a composition of multiple such compositions. 【Chemistry 1】 Here, m is between 1 and 20, n is between 1 and 20, x is between 1 and 2, and y is between 1 and 2. The liquid crystal film according to claim 2, characterized in that E and Q are acrylate, epoxy, vinyl ether, or olefin functional groups.

6. The raw material for the composite functional layer further contains a dye, The liquid crystal film according to claim 2, characterized in that the dye is an azo dye, an anthraquinone dye, or a phthalocyanine dye.

7. A method for manufacturing a liquid crystal film according to claim 2, Step S1 involves uniformly mixing each raw material, adding it between the substrates to fill the space between them, and performing the first curing by ultraviolet irradiation polymerization and / or thermal polymerization to obtain film A. Step S2 involves performing a second curing by irradiating film A with ultraviolet light at a temperature T1 for t1 hours through a photomask, under conditions where the liquid crystal material molecules in film A are oriented or not oriented, to obtain film B. Step S3 involves performing a third curing by irradiating film B with ultraviolet light at a temperature T2 for t2 hours under conditions in which the liquid crystal material molecules in film B are oriented or not oriented, thereby obtaining a liquid crystal film having an intelligent information encryption function. A manufacturing method characterized by including the following.

8. When the flexible polymerizable monomer is a flexible photopolymerizable monomer, the production method is: The steps include: uniformly mixing each raw material to form a precursor solution; adding the precursor solution between substrates to fill the space between the substrates and produce a film; and performing the first curing by irradiating the precursor solution with ultraviolet light at a temperature T1 for t1 hours through a photomask, under conditions where an electric field is applied to the film or not, to obtain film A; The steps include: obtaining a liquid crystal film having intelligent information encryption functionality by performing a second curing by irradiating film A with ultraviolet light at a temperature T2 for t2 hours under conditions in which the liquid crystal material molecules in film A are oriented or not oriented; The manufacturing method according to claim 7, characterized by including

9. The orientation is specifically controlled by applying an electric field to film A or film B, and / or In S1, if the flexible polymerizable monomer is a flexible photopolymerizable monomer, ultraviolet irradiation polymerization is employed, with a temperature of -20 to 60°C, a time of 5 to 90 s, and an ultraviolet intensity of 0.5 to 300 mW / cm². ２ If the flexible polymerizable monomer is a flexible thermal polymerizable monomer, thermal polymerization is employed, with a temperature of 20 to 120°C and a time of 0.1 to 1 hour. If the flexible polymerizable monomer is a mixture of a flexible photopolymerizable monomer and a flexible thermal polymerizable monomer, stepwise ultraviolet irradiation polymerization and thermal polymerization are performed on the flexible polymerizable monomer, and / or T1 is -20 to 60°C, t1 is 1 to 600 s, and UV intensity is 0.5 to 300 mW / cm². ２ and / or T2 is -20 to 60°C, t2 is 5 to 300 s, and UV intensity is 0.5 to 300 mW / cm². ２ The manufacturing method according to claim 7, characterized in that...

10. Use of a liquid crystal film according to any one of claims 1 to 6 or a liquid crystal film manufactured by any one of claims 7 to 9 in a patternable and adjustable device.

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