CN115785599B - Preparation method of bionic thermochromic material for hyperspectral camouflage - Google Patents
Preparation method of bionic thermochromic material for hyperspectral camouflage Download PDFInfo
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Abstract
The invention relates to a preparation method of a bionic thermochromic material for hyperspectral camouflage, and belongs to the technical field of hyperspectral camouflage. Taking polyvinyl alcohol as a base material, and taking anhydrous lithium chloride, reversible thermochromic microcapsules and inorganic monochromatic pigment particles as additive materials to obtain a color-changing mixed solution, namely a casting solution; the reversible thermochromic microcapsule is prepared from a wall material and a core material which is prepared by fully mixing a color former, a color developer, a hysteresis agent and a solvent; a coloring response temperature of-10 ℃ and a fading response temperature of 60 ℃; spreading the casting film liquid in a mould to naturally form a film, thus obtaining the thermochromic material. The thermochromic material is imitated to realize the characteristics of near infrared plateau and water absorption valley of a vegetation background which are finely imitated in a visible light-near infrared band of 400-2500 nm; when in a coloring state, the simulated thermochromic material presents a color formed by color mixing of the reversible thermochromic microcapsules and the inorganic monochromatic pigment; when in a fading state, the bionic thermochromic material presents the color of an inorganic monochromatic pigment.
Description
Technical Field
The invention belongs to the technical field of hyperspectral camouflage, and particularly relates to a preparation method of a bionic thermochromic material for hyperspectral camouflage.
Background
The hyperspectral detection technology is an important means for detecting and identifying targets in recent years, and the detection wave band is 400-2500 nm. The detection technology can be used for identifying the spectral characteristics of the object in the visible light wave band (380-780-nm) and identifying the spectral characteristics of the object in the near infrared wave band (780-2500-nm). The hyperspectral detection technology is continuously advanced, the detection resolution can reach 10 nm, the wave band number can reach more than 200, and the camouflage technology of the target is promoted to be required to be developed towards high-precision camouflage. The hyperspectral camouflage can be achieved by adopting the bionic material with the spectrum characteristics consistent with the background environment in the visible light-near infrared band. A common background environment is typically a vegetation environment. The plant leaves in the vegetation environment occupy a larger area, so the plant leaves become a main imitation object of the bionic material. The spectral features of the plant leaf include visible band spectral features and near infrared band spectral features. The visible light wave band spectral characteristics of the plant leaves are relatively high in color correlation, and are substantially correlated with different pigment contents in the plant leaves, so that the visible light wave band spectral characteristics of the plant leaves with different colors are different. Common plant leaf colors are green, yellow, orange red, etc. The visible light wave band spectrum characteristics of the green plant leaf are as follows: (1) A reflection peak exists near 550 nm and is called a green peak, and the intensity is generally 8-20%; (2) The reflectance increases sharply in the 680-780 nm wavelength range, called "red edge". The visible light wave band spectrum characteristics of the yellow plant leaf are as follows: (1) The reflectivity is lower at wavelengths less than 500 nm, and the intensity is generally less than 10%; (2) The reflectivity gradually rises in the range of 500-780 nm wave bands, which is called as a green edge. The visible light wave band spectrum characteristics of the orange-red plant leaf are as follows: the reflectance is lower at short wavelengths and gradually increases near 550 nm. The near infrared spectrum characteristics of the plant leaves with different colors show consistency: (1) The reflectivity is larger in the wavelength range of 780-1300 and nm, the intensity is generally 40-60 percent, the reflection is called a near infrared plateau, and the reflection is generated by the pore structure in the plant leaf and the high scattering of pigment particles; (2) The reflectivity is low near 1460 nm and 1940 nm, the intensities are 15-25% and 5-10%, respectively, called "water absorption valleys", which are caused by the absorption of moisture in the plant leaves. In practice, when the target is in a maneuvering state, the background environment changes along with the change of the space position, and correspondingly, the color of the plant leaves in the background environment also changes; the plant leaves in the background environment where the target is stationary will change color over time. Therefore, how to prepare the color-adjustable bionic hyperspectral camouflage material is a technical problem to be solved by the technicians in the field.
The traditional camouflage materials are generally camouflage nets, camouflage paint and the like, and the materials can realize the color consistent with the plant leaves in the visible light wave band, but cannot be matched with the spectrum of the visible light wave band of the background in high-light detection, namely the characteristic of same color spectrum cannot be realized. In view of the current situation, bionic materials with the same color and spectrum as single green plant leaves have been developed by improving the structures and components of camouflage nets and camouflage materials at home and abroad. However, the bionic material only has similar spectrum with the plant leaves in the visible light band, and the spectrum in the near infrared band has larger difference with the plant leaves, so that the bionic material cannot cope with high-precision hyperspectral detection technology. This is due to the fact that such biomimetic materials do not have the moisture characteristics of plant leaves. In view of this situation, researchers have developed a biomimetic material that mimics the reflectance spectrum of a single-color plant leaf in the visible-near infrared band, but this material can only take on static colors and cannot achieve color changes. In recent years, patent application CN 202110915133.1 truly relates to hyperspectral camouflage realized by changing the reflection spectrum of a color-changing film in the spectral range of 400-2500 nm in the visible and near infrared bands through different applied voltages, but does not give an actual simulation effect. Furthermore, the patent is directed to producing a color change by electrical stimulation, where the color does not continue to hold after the electrical stimulation is removed.
Disclosure of Invention
In order to realize that the color of a visible light wave band is changed according to the thermal stimulus, and the near infrared wave band has the reflection characteristic consistent with the vegetation background, the invention provides a preparation method of a color-changing camouflage material used in hyperspectral camouflage, so as to realize camouflage under hyperspectral detection and adapt to the vegetation background with continuously changing color in target maneuver.
The color-changing camouflage material prepared by the invention generates color change through thermal stimulation, and the color can be kept continuously after the thermal stimulation is removed, so that the energy is saved.
The preparation operation of the bionic thermochromic material adopts a solution casting method, takes polyvinyl alcohol as a base material of the bionic material, and takes metal chloride, reversible thermochromic microcapsules and monochromatic pigment particles as additive materials.
The preparation method comprises the following steps:
(1) Using polyvinyl alcohol as a substrate of a bionic material, dissolving 10 g polyvinyl alcohol particles in 500 g deionized water, heating and uniformly stirring to obtain a polyvinyl alcohol solution;
(2) Adding 2 g anhydrous lithium chloride into the polyvinyl alcohol solution, uniformly stirring, and cooling to room temperature to obtain a mixed solution;
the metal chloride refers to inorganic salt which can absorb moisture in air under the high humidity condition or desorb moisture under the low humidity condition, and the anhydrous lithium chloride powder is used in the invention;
(3) Adding 3.0-4.5 g reversible thermochromic microcapsules and 1.0-1.2 g inorganic monochromatic pigment particles into the mixed solution, stirring the mixed solution for 2 h, and uniformly mixing to obtain a color-changing mixed solution, namely a casting film solution;
the reversible thermochromic microcapsule consists of a wall material and a core material, wherein the core material is prepared by fully mixing 10 parts by mass of a color former, 20 parts by mass of a color developer, 25 parts by mass of a hysteresis agent and 45 parts by mass of a solvent;
the color-developing agent comprises red pigment-16 (3, 3-bis (N-octyl-2-methylindole) phthalide) or thermosensitive green (2 ' -anilino-6 ' - (diethylamino) spiro [ 2-benzofuran-3, 9' -xanthine ] -1-ketone);
the color developing agent is bisphenol A, bisphenol AF, diphenol or a combination thereof;
the hysteresis agent is capric acid, palmitic acid, stearic acid or a combination thereof;
the solvent is phenyl alcohol ((2- (4-phenylmethoxy) ethanol);
the color response temperature of the reversible thermochromic microcapsule is-10 ℃, and the color fading response temperature is 60 ℃, namely the temperature is heated to 60 ℃, namely the color changes from a dark color fading state to a light color fading state, the temperature is reduced to-10 ℃, and the color is restored from the light color fading state to the dark color fading state;
(4) Standing the casting solution for defoaming, pouring and spreading the casting solution in a mold, and naturally forming a film at 25-50 ℃ and humidity of 30%, thus obtaining the thermochromic material;
the bionic thermochromic material realizes the characteristics of near infrared plateau and water absorption valley of 400-2500 nm in visible light wave band and near infrared wave band to finely simulate vegetation background; when in a coloring state, the simulated thermochromic material presents a color formed by color mixing of the reversible thermochromic microcapsules and the inorganic monochromatic pigment; when in a fading state, the bionic thermochromic material presents the color of an inorganic monochromatic pigment.
Further, the reversible thermochromic microcapsule is a reversible thermochromic composition with large hysteresis characteristics embedded in a wall material. The composition is formed by compounding four components of a color former, a color developer, a solvent and a hysteresis agent, and has the memory functions of reducing temperature, developing color, increasing temperature, fading and keeping color. The color memory function means that the temperature of the color is not consistent with the temperature of the color to be dyed, and the hysteresis width (the absolute value of the temperature difference between the midpoint of the color to be dyed and the midpoint of the color to be dyed) exists. The reversible thermochromic composition with the ambient temperature within the hysteresis width is the substance embedded in the wall material of the reversible thermochromic microcapsule. As shown in fig. 1, the reversible thermochromic microcapsules can be reversibly changed between a colored state and a faded state by temperature stimulation. Reversible thermochromic microcapsules can be prepared by referring to the prior art: dispersing the core material in a continuous phase containing the wall material through an emulsification process, adding a reaction monomer and a catalyst into the continuous phase to generate a wall material prepolymer, slowly depositing the prepolymer on the surface of the core material, and forming a shell layer of a reticular high polymer structure through polycondensation to prepare the reversible thermochromic microcapsule.
The reversible thermochromic microcapsule comprises a reversible thermochromic microcapsule with a green coloring state or a reversible thermochromic microcapsule with a red coloring state;
the color former of the reversible thermochromic microcapsule with green color is thermosensitive green (2 ' -anilino-6 ' - (diethylamino) spiro [ 2-benzofuran-3, 9' -xanthine ] -1-one);
the color former of the reversible thermochromic microcapsule with red color is haematochrome-16 (3, 3-bis (N-octyl-2-methylindole) o-phthalide).
The beneficial technical effects of the invention are as follows:
the bionic thermochromic material for hyperspectral camouflage provided by the invention realizes the change between two different colors through temperature stimulation, and the colors can be kept continuously after the temperature stimulation is removed, namely, the colors can be mutually converted between stable equilibrium states. As shown in fig. 3, when the reversible thermochromic microcapsules are in a colored state, color mixture is formed with a single-color pigment; when the reversible thermochromic microcapsules are in the fade state, the material color assumes the color of the single color pigment. Thus, the imitation of the spectral characteristics of the plant leaves in the visible band in two different colours can be achieved by temperature stimulation after mixing a certain amount of reversible thermochromic microcapsules with a specific colour with a single colour pigment. "near infrared plateau" in the spectral characteristics of plant leaves in the near infrared band can be achieved by the high scattering characteristics of reversible thermochromic microcapsules and monochromatic pigment particles for light in this band. The "water absorption valleys" of the plant leaves in the spectral characteristics of the near infrared band may be achieved by metal chlorides that are capable of absorbing air moisture.
Compared with the traditional camouflage material, the bionic thermochromic material for hyperspectral camouflage can finely simulate the fine reflection spectrum of the plant leaves in the visible light-near infrared band, and overcomes the defects of the traditional camouflage, such as the characteristic of the reflection spectrum of the near infrared 'water absorption valley'.
Compared with the bionic material which can simulate the reflection spectrum of a single-color plant leaf in the visible light-near infrared band and appears in recent years, the bionic thermochromic material for hyperspectral camouflage prepared by the invention can be switched between two different colors according to the change of the background environment, has more environmental adaptability and flexibility, and meets the requirements of complex environmental backgrounds.
Compared with the existing color-changeable bionic material, the bionic thermochromic material for hyperspectral camouflage prepared by the invention can be mutually converted between a stable coloring state and a fading state, and the color change has hysteresis property, so that the energy consumption can be saved: the color of the thermochromic material can be changed under the short-term external temperature stimulation and then can be kept continuously, namely the thermochromic material is not influenced by natural environmental factors such as solar radiation, weather change, temperature fluctuation and the like after the temperature stimulation is removed. In addition, the bionic thermochromic material can expand the regulation and control range from a visible light region to a main wave band of hyperspectral detection, namely a visible light-near infrared wave band of 400-2500 nm, so that the characteristics of 'near infrared plateau' and 'water absorption valley' of a vegetation background are finely simulated.
Drawings
FIG. 1 is a schematic representation of the color change with temperature of the reversible thermochromic microcapsules used in the present invention.
Fig. 2 is a schematic flow chart of a preparation method of a bionic thermochromic material.
Fig. 3 is a color change principle of a bionic thermochromic material provided by the invention.
Fig. 4 is a reflection spectrum of the bionic thermochromic material prepared in example 1 in the visible light-near infrared band when the material is green or yellow.
Fig. 5 is a reflection spectrum of the bionic thermochromic material prepared in example 2 in the visible-near infrared band when the material is orange red or yellow.
Detailed Description
The present invention will be described in further detail by way of examples.
The sources of materials and equipment used in the following examples are described below:
polyvinyl alcohol and anhydrous lithium chloride powder produced by national pharmaceutical chemicals were used.
The color former, hysteresis agent and solvent in the core material component of the reversible thermochromic microcapsule are all purchased from the Zhonghua reagent.
The titanium chrome yellow inorganic pigment produced by the Taobao shop-Yuyao maple plastic dyeing and self-operating shop is used. Titanium chrome brown inorganic pigment produced by Changsha long chemical Co., ltd. Electric stirring was carried out using a JJ-1 electric stirrer manufactured by New Instrument Co., ltd.
Example 1
Referring to fig. 2, the procedure for preparing the thermochromic-like material by the solution casting method is as follows:
(1) At room temperature, 10 g polyvinyl alcohol and 500 g deionized water were added to a three-necked flask and placed in a heating mantle, and stirred electrically and mechanically at a stirring speed of 80 rpm/min. The temperature of the heating sleeve is set to be 90 ℃, and the polyvinyl alcohol solution is prepared after the temperature is increased to be 90 ℃ and the constant temperature stirring is kept for 1 h.
(2) 2 g anhydrous lithium chloride powder is added into the flask, stirred evenly and cooled to room temperature, and then a mixed solution is obtained.
(3) Adding 4.5 g of the reversible thermochromic microcapsule with a green coloring state and 1.1 g of the titanium chrome yellow inorganic monochromatic pigment into the mixed solution, and continuously stirring for 2 h to uniformly disperse pigment particles to form a casting film solution.
The reversible thermochromic microcapsule with a green coloring state consists of a wall material and a core material, wherein the core material is prepared by fully mixing 10 parts by mass of a color former, 20 parts by mass of a color developer, 25 parts by mass of a hysteresis agent and 45 parts by mass of a solvent:
the color-developing agent is thermosensitive green (2 ' -anilino-6 ' - (diethylamino) spiro [ 2-benzofuran-3, 9' -xanthine ] -1-ketone);
the color developing agent is bisphenol A;
the hysteresis agent is capric acid;
the solvent is phenyl alcohol ((2- (4-phenylmethoxy) ethanol).
(4) Spreading the casting solution on a mold made of polytetrafluoroethylene, and placing the mold in a constant temperature and humidity box with the temperature of 25 ℃ and the humidity of 30%, wherein the film is formed by about 36 h; thus obtaining the thermochromic material.
Referring to fig. 4, the reflectance spectra of the bionic thermochromic material prepared in example 1 were respectively measured using an ultraviolet-visible-near infrared spectrophotometer (shimadzu DUV-3700) under different colors.
The reversible thermochromic microcapsules in the bionic thermochromic material prepared in example 1 have a coloring response temperature of-10 ℃ and a fading response temperature of 60 ℃, namely have the characteristics of changing color from a dark colored state to a light colored state when heated to 60 ℃ and recovering the color from the light colored state to the dark colored state when cooled to-10 ℃. The color change principle can be seen in fig. 3, when the reversible thermochromic microcapsule is green (coloring state), the color of the reversible thermochromic microcapsule and the yellow titanium chrome yellow inorganic monochromatic pigment is mixed, and the material is green after the color mixing of the reversible thermochromic microcapsule and the titanium chrome yellow inorganic monochromatic pigment is mixed due to the fact that the mass ratio of the reversible thermochromic microcapsule to the titanium chrome yellow inorganic monochromatic pigment is large; when the reversible thermochromic microcapsule is light green (fading state), the reversible thermochromic microcapsule and the yellow titanium chrome yellow inorganic monochromatic pigment are mixed, and at the moment, the titanium chrome yellow has a large contribution to the color of the material, and the material is yellow. As can be seen from fig. 4, when the bionic thermochromic material prepared in example 1 is green, the reflection peak near 500 and nm in the visible light band can simulate the "green peak" characteristic of the green plant leaf, and the reflectance in the wavelength range of 680-780-nm increases sharply, so as to simulate the "red edge" characteristic of the green plant leaf; the reflectivity intensity in the wavelength range of 780-1300 and nm under the near infrared band is 45-60%, the characteristic of the near infrared plateau of the green plant leaf can be imitated, and the reflectivity intensities near 1460 nm and 1940 nm are respectively 17% and 7% and the characteristic of the water absorption valley of the green plant leaf can be imitated. When the bionic thermochromic material prepared in the embodiment 1 is yellow, the reflectivity is lower than 10% when the wavelength of the bionic thermochromic material is smaller than 500 nm in a visible light wave band, and the reflectivity is sharply increased in a wavelength range of 500-780 nm, so that the characteristic of simulating the green edge of a yellow plant leaf is realized; the reflectivity intensity of 780-1300 nm wavelength range under the near infrared band is 40-55%, so that the characteristic of 'near infrared plateau' imitating green plant leaves is realized, and the reflectivity intensities of 14% and 6% near 1460 nm and 1940 nm respectively can imitate the characteristic of 'water absorption valley' of the green plant leaves.
Example 2
Referring to fig. 2, the procedure for preparing the thermochromic-like material by the solution casting method is as follows:
(1) At room temperature, 10 g polyvinyl alcohol and 500 g deionized water were added to a three-necked flask and placed in a heating mantle, and stirred electrically and mechanically at a stirring speed of 80 rpm/min. The temperature of the heating sleeve is set to be 90 ℃, and the polyvinyl alcohol solution is prepared after the temperature is increased to be 90 ℃ and the constant temperature stirring is kept for 1 h.
(2) 2 g anhydrous lithium chloride powder is added into the flask, stirred evenly and cooled to room temperature, and then a mixed solution is obtained.
(3) Adding 3.0 g reversible thermochromic microcapsules with a red coloring state and 1.0 g titanium-chromium-brown inorganic monochromatic pigment into the mixed solution, and continuously stirring for 2 h to uniformly disperse pigment particles to form a casting film solution.
The reversible thermochromic microcapsule with a red coloring state consists of a wall material and a core material, wherein the core material is prepared by fully mixing 10 parts by mass of a color former, 20 parts by mass of a color developer, 25 parts by mass of a hysteresis agent and 45 parts by mass of a solvent:
the color former is red pigment-16 (3, 3-bis (N-octyl-2-methylindole) phthalide);
the color developing agent is bisphenol AF;
the hysteresis agent is palmitic acid;
the solvent is phenyl alcohol ((2- (4-phenylmethoxy) ethanol).
(4) Spreading the casting solution on a mold made of polytetrafluoroethylene, and placing the mold in a constant temperature and humidity box with the temperature of 25 ℃ and the humidity of 30%, wherein the film is formed by about 36 h; thus obtaining the thermochromic material.
Referring to fig. 5, the reflectance spectra of the bionic thermochromic material prepared in example 2 under different colors were respectively tested using an ultraviolet-visible-near infrared spectrophotometer (shimadzu DUV-3700).
The reversible thermochromic microcapsules in the bionic thermochromic material prepared in example 2 have a coloring response temperature of-10 ℃ and a fading response temperature of 60 ℃, namely have the characteristics of changing color from a dark colored state to a light colored state when heated to 60 ℃ and recovering the color from the light colored state to the dark colored state when cooled to-10 ℃. The color change principle can be seen in fig. 3, when the reversible thermochromic microcapsule is red (coloring state), the color of the reversible thermochromic microcapsule and the titanium-chromium-brown inorganic monochromatic pigment which presents yellow color are mixed, and the material presents orange red after the color mixture of the reversible thermochromic microcapsule and the titanium-chromium-brown inorganic monochromatic pigment because the former has larger mass; when the reversible thermochromic microcapsule is light red (fading state), the color of the reversible thermochromic microcapsule is mixed with the titanium chrome brown inorganic monochromatic pigment which presents yellow, and at the moment, the contribution of the titanium chrome brown to the color of the material is large, and the material presents yellow. As can be seen from fig. 5, when the bionic thermochromic material prepared in example 2 is orange red, the reflectivity is lower than 10% and the reflectivity is sharply increased in the wavelength range of 550-700 nm when the wavelength is smaller than 550 nm in the visible light band, so as to simulate the spectral characteristics of the orange red plant leaf in the visible light band; the reflectivity intensity of 780-1300 and nm wavelength ranges in the near infrared band is 45-55%, so that the characteristic of 'near infrared plateau' imitating orange-red plant leaves is realized, and the reflectivity intensities near 1460 nm and 1940 nm are respectively 16% and 6% respectively, so that the characteristic of 'water absorption valley' imitating green plant leaves can be realized. When the bionic thermochromic material prepared in the embodiment 2 is yellow, the reflectivity is lower than 10% when the wavelength of the bionic thermochromic material is smaller than 480 nm in the visible light wave band, and the reflectivity is sharply increased in the wavelength range of 500-780 nm, so that the characteristic of simulating the green edge of a yellow plant leaf is realized; the reflectivity intensity of 780-1300 and nm wavelength ranges under the near infrared band is 40-50%, the near infrared plateau characteristic imitating the green plant leaf is realized, the reflectivity intensities near 1460 nm and 1940 nm are respectively 15% and 6%, and the water absorption valley characteristic imitating the green plant leaf is realized.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or changes may be made within the spirit and principles of the invention.
Claims (6)
1. A preparation method of a bionic thermochromic material for hyperspectral camouflage is characterized by comprising the following steps: polyvinyl alcohol is used as a substrate of a bionic material, and metal chloride, reversible thermochromic microcapsules and inorganic monochromatic pigment particles are used as additive materials;
the specific operation steps are as follows:
(1) Using polyvinyl alcohol as a substrate of a bionic material, dissolving 10 g polyvinyl alcohol particles in 500 g deionized water, heating and uniformly stirring to obtain a polyvinyl alcohol solution;
(2) Adding 2 g metal chloride into the polyvinyl alcohol solution, uniformly stirring, and cooling to room temperature to obtain a mixed solution;
(3) Adding 3.0-4.5 g reversible thermochromic microcapsules and 1.0-1.2 g inorganic monochromatic pigment particles into the mixed solution, stirring the mixed solution for 2 h, and uniformly mixing to obtain a color-changing mixed solution, namely a casting film solution;
the reversible thermochromic microcapsule consists of a wall material and a core material, wherein the core material is prepared by fully mixing 10 parts by mass of a color former, 20 parts by mass of a color developer, 25 parts by mass of a hysteresis agent and 45 parts by mass of a solvent;
the color-developing agent comprises red pigment-16 (3, 3-bis (N-octyl-2-methylindole) phthalide) or thermosensitive green (2 ' -anilino-6 ' - (diethylamino) spiro [ 2-benzofuran-3, 9' -xanthine ] -1-ketone);
the color developing agent is bisphenol A, bisphenol AF, diphenol or a combination thereof;
the hysteresis agent is capric acid, palmitic acid, stearic acid or a combination thereof;
the solvent is 2- (4-phenylmethoxy) ethanol;
the color response temperature of the reversible thermochromic microcapsule is-10 ℃, and the color fading response temperature is 60 ℃, namely the temperature is heated to 60 ℃, namely the color changes from a dark color fading state to a light color fading state, the temperature is reduced to-10 ℃, and the color is restored from the light color fading state to the dark color fading state;
(4) Standing the casting solution for defoaming, pouring and spreading the casting solution in a mold, and forming a film under certain temperature and humidity conditions to obtain the thermochromic material;
the bionic thermochromic material realizes the characteristics of near infrared plateau and water absorption valley of 400-2500 nm in visible light wave band and near infrared wave band to finely simulate vegetation background; when in a coloring state, the simulated thermochromic material presents a color formed by color mixing of the reversible thermochromic microcapsules and the inorganic monochromatic pigment; when in a fading state, the bionic thermochromic material presents the color of an inorganic monochromatic pigment.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the constant temperature stirring is kept for 1 h under the condition that the temperature is increased to 90 ℃ and the rotating speed is 80 rpm/min.
3. The method of manufacturing according to claim 1, characterized in that: in the step (2), the metal chloride is an inorganic salt capable of absorbing moisture in air under a high humidity condition or desorbing moisture under a low humidity condition, and the inorganic salt is anhydrous lithium chloride powder.
4. The method of manufacturing according to claim 1, characterized in that: in the step (3), the inorganic monochromatic pigment is iron oxide green, chromium oxide green, green nickel oxide, titanium nickel yellow, titanium chrome brown, iron oxide yellow, titanium chrome yellow, iron oxide red, cadmium red and molybdenum chrome red.
5. The method of manufacturing according to claim 1, characterized in that: in the step (3), the reversible thermochromic microcapsule comprises a reversible thermochromic microcapsule with a green coloring state or a reversible thermochromic microcapsule with a red coloring state;
the color former of the reversible thermochromic microcapsule with green color is thermosensitive green (2 ' -anilino-6 ' - (diethylamino) spiro [ 2-benzofuran-3, 9' -xanthine ] -1-one);
the color former of the reversible thermochromic microcapsule with red color is haematochrome-16 (3, 3-bis (N-octyl-2-methylindole) o-phthalide).
6. The method of manufacturing according to claim 1, characterized in that: in the step (4), film formation is carried out in a constant temperature and humidity box under the conditions of 25-50 ℃ and 30% humidity.
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