Patterned electric heating material and preparation method and application thereof

Abstract

The invention relates to the technical field of electric heating components, and discloses a patterned electric heating material and a preparation method and application thereof.The patterned electric heating material sequentially comprises a heating protection layer and a thermochromic layer from bottom to top, the heating protection layer comprises a heating layer and a protection layer which are sequentially stacked, and the protection layer is arranged on the upper surface of the heating layer; the number of the heating protection layer is one or more; the heating layer is prepared by curing a mixed solution comprising silver nanowires and hydroxypropyl methyl cellulose and then performing laser etching on patterns; the protective layer is prepared by curing a polyimide coating; and the thermochromic layer is prepared by curing thermochromic liquid crystal ink. By adopting the patterned electric heating material provided by the invention, different patterns can be respectively displayed, and different patterns can be simultaneously displayed, so that the patterned electric heating material is suitable for wide popularization and application.

Description

Technical Field

[0001] The present invention belongs to the technical field of electric heating components, and in particular relates to a patterned electric heating material and a preparation method and application thereof. Background Art

[0002] Traditional electrothermal materials usually focus on the overall heating function and have a single application scenario. The existing technology patterns the silver nanowire electrothermal materials. Since the silver nanowires have excellent electrical conductivity, softness, stretchability, and high transparency, the electrothermal devices have a high electrothermal conversion efficiency; they can adapt to various complex shapes and curved surfaces, and are suitable for wearable devices, flexible display screens, and other fields; while maintaining good electrical conductivity, they can also achieve high transparency, and are suitable for optical applications such as touch screens and display panels.

[0003] The patent technology with publication number CN 110351904 A discloses a thermal imaging patterned electric heating device and an electric heating product, wherein the electric heating device comprises a heating layer and a protective layer, wherein the heating layer is a thermal imaging patterned heating layer; and / or the protective layer is a thermal imaging patterned protective layer. Taking Example 1 as an example, the preparation method is as follows: (1) using a PET film 1 as a substrate, using a sticker to cover the area to be hollowed out on the PET film 1, wherein the hollowed out areas are a square, a circle and a triangle respectively; (2) applying carbon crystal conductive ink on the surface of the substrate on the PET film 1 covered with the sticker by coating; (3) after the carbon crystal conductive ink is dried, removing the sticker, i.e., a thermal imaging patterned electric heating layer 3 having a hollowed out area 2 is formed on the surface of the PET film 1. The electric heating device prepared by the patent can produce thermal imaging patterns, but the patterning response effect is single: when a single layer is patterned, only the three patterns of triangle (1), circle (2), and square (3) can appear or disappear at the same time, and it is impossible to achieve the three patterns of triangle (1), circle (2), and square (3) to appear separately, or it is impossible to appear two of them. Figure 1 When multi-layer patterning is performed, only the three patterns of triangle (1), circle (2), and square (3) can be realized to appear separately, and it is impossible to realize the three patterns of triangle (1), circle (2), and square (3) to appear at the same time. Figure 2 . Summary of the invention

[0004] The present invention provides a patterned electrothermal material and a preparation method and application thereof, which solves the problem that the electrothermal device prepared by the prior art can generate thermal imaging patterns, but the pattern response effect is single: when a single layer is patterned, only multiple patterns can be achieved to appear or disappear at the same time, and it is impossible to achieve a single pattern, or two of them cannot appear; when a multi-layer is patterned, only multiple patterns can be achieved to appear separately, and it is impossible to achieve multiple patterns to appear at the same time.

[0005] A first aspect of the present invention provides a patterned electrothermal material, which comprises, from bottom to top, a heating protection layer and a thermochromic layer stacked in sequence;

[0006] The heating protection layer is a stacked heating layer and a protection layer, and the protection layer is arranged on the upper surface of the heating layer;

[0007] The heating protection layer is one or more layers;

[0008] The heating layer is made by curing a mixed solution of silver nanowires and hydroxypropyl methylcellulose and then laser etching a pattern; the protective layer is made by curing a polyimide coating; and the thermochromic layer is made by curing a thermochromic liquid crystal ink.

[0009] In the present invention, the mixed solution comprising silver nanowires and hydroxypropyl methylcellulose refers to a mixed solution obtained by mixing silver nanowires and hydroxypropyl methylcellulose in a solvent.

[0010] It should be noted that the present invention does not particularly limit the specific pattern of laser etching, which can be selected according to actual needs.

[0011] The patterned electrothermal material as described above further comprises a backlight layer, which is arranged on the surface of the heating protection layer close to the thermochromic layer; the backlight layer is made of black ink by thermal curing.

[0012] The patterned electrothermal material as described above, wherein the thickness of the heating layer is 1 μm to 6 μm;

[0013] And / or, the thickness of the protective layer is 4 μm to 18 μm;

[0014] And / or, the thickness of the thermochromic layer is 15 μm to 25 μm;

[0015] And / or, the backlight layer has a thickness of 3 μm to 8 μm.

[0016] The second aspect of the present invention provides a method for preparing the patterned electrothermal material, when the heating protection layer is a layer, comprising:

[0017] Mixing silver nanowires and hydroxypropyl methylcellulose in a solvent to obtain a mixed solution, coating the mixed solution on the surface of a substrate, forming a thin film through a first curing, and then forming a pattern through laser etching on the thin film to obtain a heating layer;

[0018] Coating a polyimide coating on the surface of the heating layer away from the substrate, and forming a protective layer through a second curing, or coating a polyimide coating on the surface of the heating layer away from the substrate, and forming a protective layer through a second curing, and then coating a black ink on the surface of the protective layer away from the heating layer, and forming a backlight layer through a first thermal curing;

[0019] Coating thermochromic liquid crystal ink on the surface of the protective layer away from the heating layer, and forming a patterned electrothermal material including a thermochromic layer through a third curing process; or coating thermochromic liquid crystal ink on the surface of the backlight layer away from the protective layer, and forming a patterned electrothermal material including a thermochromic layer through a third curing process;

[0020] Wherein, the heating protection layer includes the heating layer and the protection layer.

[0021] In the method for preparing the patterned electrothermal material as described above, when preparing the film, the concentration of the silver nanowires after mixing is 25 mg / L, and the concentration of hydroxypropyl methylcellulose is 4 mg / mL.

[0022] In the method for preparing the patterned electrothermal material as described above, the solvent is at least one of deionized water, ethanol, and isopropanol.

[0023] The method for preparing the patterned electrothermal material as described above, wherein the first curing temperature is 10° C. to 200° C. and the curing time is 0.1 h to 1 h;

[0024] And / or, the second curing temperature is 10°C to 100°C and the time is 1h to 5h;

[0025] And / or, the third curing temperature is 10°C to 100°C and the time is 10min to 90min;

[0026] And / or, the temperature of the first thermal curing is 10° C. to 80° C., and the time is 3 min to 20 min.

[0027] The method for preparing the patterned electrothermal material as described above, when the heating protection layer is multi-layered, comprises:

[0028] Mixing silver nanowires and hydroxypropyl methylcellulose in a solvent to obtain a mixed solution, coating the mixed solution on the surface of a substrate, forming a first film through a fourth curing step, and then etching the first film through laser etching to form a pattern A, thereby obtaining a first heating layer;

[0029] Coating a polyimide coating on the surface of the first heating layer away from the substrate, and forming a first protective layer through a fifth curing process;

[0030] The mixed solution is coated on the surface of the first protective layer away from the first heating layer, and a second film is formed by the sixth curing, and then the second film is formed into a pattern B by laser etching to obtain a second heating layer;

[0031] Coating a polyimide coating on the surface of the second heating layer away from the first protective layer, and performing seventh curing to form a second protective layer;

[0032] The mixed solution is coated on the surface of the second protective layer away from the second heating layer, and a third thin film is formed by the eighth curing, and then the third thin film is formed into a pattern C by laser etching to obtain a third heating layer;

[0033] Coating a polyimide coating on a surface of the third heating layer away from the second protective layer, and performing a ninth curing to form a third protective layer; or coating a polyimide coating on a surface of the third heating layer away from the second protective layer, and performing a ninth curing to form a third protective layer, and then coating a black ink on a surface of the third protective layer away from the third heating layer, and performing a second thermal curing to form a backlight layer;

[0034] Coating thermochromic liquid crystal ink on the surface of the third protective layer away from the third heating layer, and forming a patterned electrothermal material including a thermochromic layer through the tenth curing, or coating thermochromic liquid crystal ink on the surface of the backlight layer away from the protective layer, and forming a patterned electrothermal material including a thermochromic layer through the third curing;

[0035] Wherein, the heating layer includes the first heating layer, the second heating layer and the third heating layer, and the protective layer includes the first protective layer, the second protective layer and the third protective layer;

[0036] The heating protective layer includes the heating layer and the protective layer.

[0037] In the present invention, the above-mentioned substrate refers to an ITO electrode.

[0038] It should be noted that, the descriptions involving “first”, “second”, “third”, “fourth”, etc. in the present invention are only for descriptive purposes and therefore cannot be understood as limiting the present invention.

[0039] In the method for preparing the patterned electrothermal material as described above, the temperatures of the fourth curing, the sixth curing and the eighth curing are all 10° C. to 200° C., and the times are all 0.1 h to 1 h;

[0040] And / or, the fifth curing, the seventh curing and the ninth curing are all performed at a temperature of 10° C. to 100° C. and for a time of 1 hour to 5 hours;

[0041] And / or, the temperature of the tenth curing is 10°C to 100°C and the time is 10h to 90min;

[0042] And / or, the temperature of the second thermal curing is 10° C. to 80° C., and the time is 3 min to 20 min.

[0043] And / or, in the mixed solution, the concentration of the silver nanowires is 10 mg / L to 100 mg / L, and the concentration of the hydroxypropyl methylcellulose is 1 mg / L to 10 mg / mL;

[0044] And / or, the solvent is at least one of deionized water, ethanol, and isopropanol.

[0045] A third aspect of the present invention provides a camouflage device, comprising the above-mentioned patterned electrothermal material.

[0046] In the present invention, the above numerical range should be understood to also specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value in the stated range and any other stated value or intermediate value in the stated range is also included, and the upper and lower limits of the smaller range can be independently included or excluded in the range.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The patterned electrothermal material provided by the prior art is non-conductive at the pattern and conductive at other parts. After power is applied, the shape at the pattern can be displayed. However, since the whole piece is heated, if it is stacked to prepare multiple layers, the pattern displayed by one layer will be covered by the conductive parts of other layers after stacking. Under visible light conditions, the transparent material can display the pattern, but under infrared conditions, the pattern at the covered part cannot be displayed. The patterned electrothermal material provided by the present invention is conductive at the pattern and non-conductive at other parts. After power is applied, the shape at the pattern can be displayed. Under visible light and infrared light, respectively, the thermochromic layer located at the top layer can form a pattern.

[0049] By using the patterned electrothermal material provided by the present invention, different patterns (such as pattern 4, pattern 5, pattern 6, pattern 7, pattern 8 and pattern 9 in Example 4) can be displayed separately, and different patterns (such as pattern 4, pattern 5, pattern 6, pattern 7, pattern 8 and pattern 9 in Example 4) can also be displayed simultaneously, which is suitable for wide promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a schematic diagram of the surface structure of a single-layer thermal imaging patterned heating layer of a thermal imaging patterned electric heating device prepared in Comparative Example 1;

[0051] Figure 2This is a schematic diagram of the surface structure of the multi-layer thermal imaging patterned heating layer of the thermal imaging patterned electric heating device prepared in Comparative Example 1;

[0052] Figure 3 is a cross-sectional view of a patterned electrothermal material prepared in Example 3 of the present invention;

[0053] Figure 4 Schematic diagrams of test results of the patterned electrothermal material prepared in Example 4 of the present invention under visible light and infrared light respectively;

[0054] in, Figure 4 A is a pattern of "D" formed under visible light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3, B is a pattern of "D" formed under infrared light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3, C is a pattern of "U" formed under visible light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3, D is a pattern of "U" formed under infrared light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3, E is a pattern of "T" formed under visible light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3, and F is a pattern of "T" formed under infrared light after applying a voltage of 2V to the patterned electrothermal material prepared in Example 3;

[0055] Figure 5 This is a schematic structural diagram of a patterned electrothermal material obtained in Example 4 of the present invention;

[0056] Figure 6 The camouflage device with multi-layer pattern imitating color-changing skin prepared by the present invention;

[0057] Figure 7 A 2V voltage is applied to the regions of the ITO electrodes 4', 5', 8' and 9' to form an "X" image;

[0058] in, Figure 7 A is the "X" pattern formed under visible light. Figure 7 B is the "X" pattern formed under infrared light;

[0059] Figure 8 A 2V voltage is applied to the regions of the ITO electrodes 4', 8' and 9' to form a "y" image;

[0060] in, Figure 8 A is the "y" pattern formed under visible light, Figure 8 B is a "y" pattern formed under infrared light;

[0061] Fig. 9 To form a 2V voltage applied to the ITO electrodes 5', 6', 7' and 9' image;

[0062] in, Fig. 9 A is formed under visible light The pattern, Fig. 9 B is formed under infrared light Patterns;

[0063] Fig.10 To form a 2V voltage applied to the regions of the ITO electrodes 4', 5', 6', 7', 8' and 9' image;

[0064] in, Fig.10 A is formed under visible light The pattern, Fig.10 B is formed under infrared light pattern. DETAILED DESCRIPTION

[0065] The technical solutions in the present invention will be described clearly and completely below in conjunction with the specific implementation of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0066] The methods described in the embodiments of the present invention are conventional methods unless otherwise specified. The materials, reagents, etc. used can be obtained from commercial sources unless otherwise specified.

[0067] In the following description of this embodiment, the order of serial numbers does not mean the order of execution. Some or all of the steps can be executed in parallel or one after the other. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of this embodiment.

[0068] Unless otherwise stated, the technical / scientific terms used in the present embodiment have the same meanings as those generally understood by those skilled in the art to which the present application belongs. Although the present application only describes preferred methods and materials, any similar or equivalent methods and materials may also be used in the implementation or testing of the present application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of any conflict with any incorporated document, the content of this specification shall prevail.

[0069] Example 1

[0070] This embodiment provides a method for preparing a patterned electrothermal material, comprising:

[0071] S1. Mix silver nanowires (AgNWs) and hydroxypropyl methylcellulose (HPMC) in deionized water to obtain a mixed solution. After the mixed solution is fully shaken in a centrifuge, 200 μL of the mixed solution is coated on the surface of the substrate (ITO electrode) at a speed of 75 mm / s, and then cured at 120°C for 50 min to form a thin film. The film is then laser etched to form a pattern including three letters "D", "U" and "T" to obtain a heating layer with a thickness of 1.5 μm. Among them, the concentration of silver nanowires after mixing is 25 mg / L, and the concentration of hydroxypropyl methylcellulose is 4 mg / mL.

[0072] The laser etching method is:

[0073] Draw on the laser machine and design the pattern on the electrothermal material. Etch with an etching power of 4W, an etching speed of 1000mm / s, an etching frequency of 80.000kHz, a laser walking spacing of 0.04mm, and a laser wavelength of 266nm.

[0074] S2. Coat the polyimide coating on the surface of the heating layer away from the substrate (ITO electrode) at a speed of 25 mm / s, and cure at 80° C. for 2 h to obtain a protective layer with a thickness of 5 μm.

[0075] S3. Coat the thermochromic liquid crystal ink on the surface of the protective layer away from the heating layer at a speed of 25 mm / s, and heat cure at 60° C. for 20 min to obtain a thermochromic layer with a thickness of 20 μm. The whole is a patterned electrothermal material.

[0076] The heating protective layer comprises a heating layer and a protective layer.

[0077] Example 2

[0078] This embodiment provides a method for preparing a patterned electrothermal material, comprising:

[0079] S1. Mix silver nanowires (AgNWs) and hydroxypropyl methylcellulose (HPMC) in deionized water to obtain a mixed solution. After the mixed solution is fully shaken in a centrifuge, 200 μL of the mixed solution is coated on the surface of the substrate (ITO electrode) at a speed of 75 mm / s, and then cured at 150°C for 50 min to form a thin film. The thin film is then laser etched to form a pattern of three letters including "D", "U" and "T" to obtain a heating layer with a thickness of 2 μm. Among them, the concentration of silver nanowires after mixing is 25 mg / L, and the concentration of hydroxypropyl methylcellulose is 4 mg / mL.

[0080] The laser etching method is:

[0081] Draw on the laser machine and design the pattern on the electrothermal material. Etch with an etching power of 4W, an etching speed of 1000mm / s, an etching frequency of 80.000kHz, a laser walking spacing of 0.04mm, and a laser wavelength of 355nm.

[0082] S2. Coat the polyimide coating on the surface of the heating layer away from the substrate (ITO electrode) at a speed of 25 mm / s, and cure at 100° C. for 2 h to obtain a protective layer with a thickness of 5.5 μm.

[0083] S3. Coat the surface of the protective layer away from the heating layer with the thermochromic liquid crystal ink at a speed of 25 mm / s, and cure it at 80° C. for 20 min to obtain a thermochromic layer with a thickness of 23 μm. The whole is a patterned electrothermal material.

[0084] The heating protective layer comprises a heating layer and a protective layer.

[0085] Example 3

[0086] This embodiment provides a method for preparing a patterned electrothermal material, comprising:

[0087] S1. Mix silver nanowires (AgNWs) and hydroxypropyl methylcellulose (HPMC) in ethanol to obtain a mixed solution. After the mixed solution is fully shaken in a centrifuge, 200 μL of the mixed solution is coated on the surface of the substrate (ITO electrode) at a speed of 75 mm / s, and then cured at 120°C for 50 minutes to form a thin film. The film is then laser etched to form a pattern including three letters "D", "U" and "T" to obtain a heating layer with a thickness of 1.5 μm. Among them, the concentration of silver nanowires after mixing is 25 mg / L, and the concentration of hydroxypropyl methylcellulose is 4 mg / mL.

[0088] The laser etching method is:

[0089] Draw on the laser machine and design the pattern on the electrothermal material. Etch with an etching power of 4W, an etching speed of 1000mm / s, an etching frequency of 80.000kHz, a laser walking spacing of 0.04mm, and a laser wavelength of 266nm.

[0090] S2. Coat the polyimide coating on the surface of the heating layer away from the substrate (ITO electrode) at a speed of 25 mm / s, and cure at 80° C. for 2 h to obtain a protective layer with a thickness of 5 μm.

[0091] S3. Apply black ink on the surface of the protective layer away from the heating layer at a speed of 25 mm / s, and heat cure at 60° C. for 5 minutes to obtain a backlight layer with a thickness of 25 μm.

[0092] S4. Coat the thermochromic liquid crystal ink on the surface of the backlight layer away from the protective layer at a speed of 25 mm / s, and cure it at 60° C. for 20 min to obtain a thermochromic layer with a thickness of 20 μm. The whole is a patterned electrothermal material.

[0093] The heating protective layer comprises a heating layer and a protective layer.

[0094] Example 4

[0095] This embodiment provides a method for preparing a patterned electrothermal material, comprising:

[0096] S1. Silver nanowires (AgNWs) and hydroxypropyl methylcellulose (HPMC) were mixed in isopropanol to obtain a mixed solution. After the mixed solution was fully shaken in a centrifuge, 200 μL of the solution was coated on the surface of the substrate (ITO electrode) at a speed of 75 mm / s, and then cured at 120°C for 50 min to form a thin film, and then the thin film was laser etched to form pattern A (including pattern 4 and pattern 5) to obtain a first heating layer with a thickness of 1.5 μm. Among them, the concentration of silver nanowires after mixing is 25 mg / L, and the concentration of hydroxypropyl methylcellulose is 4 mg / mL.

[0097] The laser etching method is:

[0098] Draw on the laser machine and design the pattern on the electrothermal material. Etch with an etching power of 4W, an etching speed of 1000mm / s, an etching frequency of 80.000kHz, a laser walking spacing of 0.04mm, and a laser wavelength of 375nm.

[0099] S2. Coat the polyimide coating on the surface of the heating layer away from the substrate (ITO electrode) at a speed of 25 mm / s, and cure at 80° C. for 2 h to obtain a first protective layer with a thickness of 5 μm.

[0100] S3, the surface of the first protective layer prepared in S2 away from the first heating layer is cured again according to the method of S1, and the film is laser etched to form a 1.5 μm pattern B (including pattern 6 and pattern 7) to obtain a second heating layer.

[0101] S4. Coat the polyimide coating on the surface of the second heating layer away from the first protective layer at a speed of 25 mm / s, and cure it at 80° C. for 2 h to obtain a second protective layer with a thickness of 5 μm.

[0102] S5. The surface of the second protective layer prepared in S4 away from the second heating layer is cured again according to the method of S1, and the film is laser etched to form a 1.5 μm pattern C (including pattern 8 and pattern 9) to obtain a third heating layer.

[0103] S6. Coat the polyimide coating on the surface of the third heating layer away from the second protective layer at a speed of 25 mm / s, and cure it at 80° C. for 2 h to obtain a third protective layer with a thickness of 5 μm.

[0104] S7, coating the black ink on the surface of the third protective layer away from the third heating layer at a speed of 25 mm / s, and thermally curing at 60° C. for 5 min to obtain a backlight layer with a thickness of 25 μm;

[0105] S8, coating the thermochromic liquid crystal ink on the surface of the backlight layer away from the third protective layer at a speed of 25 mm / s, and curing at 60° C. for 20 min to obtain a thermochromic layer with a thickness of 20 μm. Figure 5 The patterned electrothermal material shown.

[0106] The heating layer includes a first heating layer, a second heating layer and a third heating layer, and the protective layer includes a first protective layer, a second protective layer and a third protective layer;

[0107] The heating protective layer comprises a heating layer and a protective layer.

[0108] Comparative Example 1

[0109] A thermal imaging patterned electric heating device uses a PET film as a protective layer and a carbon crystal conductive ink as a heating layer material. The specific preparation steps are as follows:

[0110] (1) Using a PET film as a substrate, a sticker is used to cover the area on the surface of the PET film to be hollowed out, wherein the hollowed-out areas are respectively a square, a circle, and a triangle;

[0111] (2) applying the carbon crystal conductive ink on the surface of the PET film covered with the sticker by coating;

[0112] (3) After the carbon crystal conductive ink is dried, the sticker is removed, and a thermal imaging patterned electric heating layer with a hollow area is formed on the surface of the PET film. Figure 1 .

[0113] test

[0114] (1) Figure 3 This is a cross-sectional view of the patterned electrothermal material prepared in Example 3.

[0115] Depend on Figure 3 It can be seen that, looking from bottom to top, the first layer is the substrate (ITO electrode), the second layer is the heating layer, the third layer is the protective layer, the fourth layer is the backlight layer, and the fifth layer is the thermochromic layer.

[0116] (2) Figure 4Schematic diagrams of test results of the patterned electrothermal material prepared in Example 3 of the present invention under visible light and infrared light, respectively, wherein A is a pattern of "D" formed under visible light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3, B is a pattern of "D" formed under infrared light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3, C is a pattern of "U" formed under visible light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3, D is a pattern of "U" formed under infrared light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3, E is a pattern of "T" formed under visible light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3, and F is a pattern of "T" formed under infrared light after applying a 2V voltage to the patterned electrothermal material prepared in Example 3.

[0117] Depend on Figure 4 It can be seen from AF that the patterned electrothermal material provided in Example 3 of the present invention can achieve the appearance of a single pattern.

[0118] (3) Figure 5 This is a schematic diagram of the structure of the patterned electrothermal material prepared in Example 4.

[0119] Depend on Figure 5 It can be seen that, looking from bottom to top, the first layer is the substrate (ITO electrode), the second layer is the first heating layer, the third layer is the first protective layer, the fourth layer is the second heating layer, the fifth layer is the second protective layer, the sixth layer is the third heating layer, the seventh layer is the third protective layer, the eighth layer is the backlight layer, and the ninth layer is the thermochromic layer.

[0120] Among them, 6 areas are set for the ITO electrode, namely: 4', 5', 6', 7', 8', 9', see Figure 5 shown.

[0121] (4) Multi-layer patterned camouflage device imitating color-changing skin

[0122] The patterned electrothermal material prepared in Example 4 of the present invention is formed into a Figure 6 The multi-layer patterned camouflage device imitating color-changing skin is shown.

[0123] The chameleon skin-like multi-layer patterned camouflage device was tested, and the test results are as follows: Figure 7-10 As shown;

[0124] Figure 7 A 2V voltage is applied to the regions of the ITO electrodes 4', 5', 8' and 9' to form an "X" image, wherein: Figure 7 A is the "X" pattern formed under visible light. Figure 7 B is the "X" pattern formed under infrared light;

[0125] Figure 8 A 2V voltage is applied to the regions of the ITO electrodes 4', 8' and 9' to form a "y" image, wherein: Figure 8 A is the "y" pattern formed under visible light, Figure 8 B is a "y" pattern formed under infrared light;

[0126] Fig. 9 To form a 2V voltage applied to the ITO electrodes 5', 6', 7' and 9' Image, where Fig. 9 A is formed under visible light The pattern, Fig. 9 B is formed under infrared light Patterns;

[0127] Fig.10 To form a 2V voltage applied to the regions of the ITO electrodes 4', 5', 6', 7', 8' and 9' Image, where Fig.10 A is formed under visible light The pattern, Fig.10 B is formed under infrared light pattern.

[0128] Depend on Figure 7-10 It can be seen that the patterned electrothermal material prepared in Example 4 of the present invention can realize the appearance of pattern 4, pattern 5, pattern 6, pattern 7, pattern 8 and pattern 9 separately, and can also realize the appearance of pattern 4, pattern 5, pattern 6, pattern 7, pattern 8 and pattern 9 simultaneously.

[0129] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0130] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A patterned electrothermal material, characterized in that: It includes a heating protection layer and a thermochromic layer stacked from bottom to top; The heating protection layer is a stacked heating layer and a protection layer, and the protection layer is arranged on the upper surface of the heating layer; The heating protection layer is one or more layers; The heating layer is made by curing a mixed solution of silver nanowires and hydroxypropyl methylcellulose and then laser etching a pattern; the protective layer is made by curing a polyimide coating; and the thermochromic layer is made by curing a thermochromic liquid crystal ink.

2. The patterned electrothermal material according to claim 1, characterized in that: The patterned electrothermal material further comprises a backlight layer, which is arranged on a surface of the heating protection layer close to the thermochromic layer; the backlight layer is made of black ink through thermal curing.

3. The patterned electrothermal material according to claim 2, characterized in that: The thickness of the heating layer is 1 μm to 6 μm; And / or, the thickness of the protective layer is 4 μm to 18 μm; And / or, the thickness of the thermochromic layer is 15 μm to 25 μm; And / or, the backlight layer has a thickness of 3 μm to 8 μm.

4. A method for preparing a patterned electrothermal material according to any one of claims 1 to 3, characterized in that: When the heating protection layer is a single layer, it comprises: Mixing silver nanowires and hydroxypropyl methylcellulose in a solvent to obtain a mixed solution, coating the mixed solution on the surface of a substrate, forming a thin film through a first curing, and then forming a pattern through laser etching on the thin film to obtain a heating layer; Coating a polyimide coating on the surface of the heating layer away from the substrate, and forming a protective layer through a second curing, or coating a polyimide coating on the surface of the heating layer away from the substrate, and forming a protective layer through a second curing, and then coating a black ink on the surface of the protective layer away from the heating layer, and forming a backlight layer through a first thermal curing; Coating thermochromic liquid crystal ink on the surface of the protective layer away from the heating layer, and forming a patterned electrothermal material including a thermochromic layer through a third curing process; or coating thermochromic liquid crystal ink on the surface of the backlight layer away from the protective layer, and forming a patterned electrothermal material including a thermochromic layer through a third curing process; Wherein, the heating protection layer includes the heating layer and the protection layer.

5. The method for preparing the patterned electrothermal material according to claim 4, characterized in that: In the mixed solution, the concentration of the silver nanowires is 10 mg / L to 100 mg / L, and the concentration of the hydroxypropyl methylcellulose is 1 mg / L to 10 mg / mL.

6. The method for preparing the patterned electrothermal material according to claim 4, characterized in that: The solvent is at least one of deionized water, ethanol and isopropanol.

7. The method for preparing the patterned electrothermal material according to claim 4, characterized in that: The first curing temperature is 10°C to 200°C and the time is 0.1h to 1h; And / or, the second curing temperature is 10°C to 100°C and the time is 1h to 5h; And / or, the third curing temperature is 10°C to 100°C and the time is 10min to 90min; And / or, the temperature of the first thermal curing is 10° C. to 80° C., and the time is 3 min to 20 min.

8. The method for preparing a patterned electrothermal material according to claim 4, characterized in that: When the heating protection layer is multi-layer, it includes: Mixing silver nanowires and hydroxypropyl methylcellulose in a solvent to obtain a mixed solution, coating the mixed solution on the surface of a substrate, forming a first film through a fourth curing step, and then etching the first film through laser etching to form a pattern A, thereby obtaining a first heating layer; Coating a polyimide coating on the surface of the first heating layer away from the substrate, and forming a first protective layer through a fifth curing process; The mixed solution is coated on the surface of the first protective layer away from the first heating layer, and a second film is formed by the sixth curing, and then the second film is formed into a pattern B by laser etching to obtain a second heating layer; Coating a polyimide coating on the surface of the second heating layer away from the first protective layer, and performing seventh curing to form a second protective layer; The mixed solution is coated on the surface of the second protective layer away from the second heating layer, and a third thin film is formed by the eighth curing, and then the third thin film is formed into a pattern C by laser etching to obtain a third heating layer; Coating a polyimide coating on a surface of the third heating layer away from the second protective layer, and performing a ninth curing to form a third protective layer; or coating a polyimide coating on a surface of the third heating layer away from the second protective layer, and performing a ninth curing to form a third protective layer, and then coating a black ink on a surface of the third protective layer away from the third heating layer, and performing a second thermal curing to form a backlight layer; Coating thermochromic liquid crystal ink on the surface of the third protective layer away from the third heating layer, and forming a patterned electrothermal material including a thermochromic layer through the tenth curing, or coating thermochromic liquid crystal ink on the surface of the backlight layer away from the protective layer, and forming a patterned electrothermal material including a thermochromic layer through the third curing; Wherein, the heating layer includes the first heating layer, the second heating layer and the third heating layer, and the protective layer includes the first protective layer, the second protective layer and the third protective layer; The heating protective layer includes the heating layer and the protective layer.

9. The method for preparing a patterned electrothermal material according to claim 8, characterized in that: The fourth curing, the sixth curing and the eighth curing are all performed at temperatures of 10° C. to 200° C. and for a time of 0.1 h to 1 h; And / or, the fifth curing, the seventh curing and the ninth curing are all performed at a temperature of 10° C. to 100° C. and for a time of 1 hour to 5 hours; And / or, the temperature of the tenth curing is 10°C to 100°C and the time is 10h to 90min; And / or, the temperature of the second thermal curing is 10° C. to 80° C., and the time is 3 min to 20 min. And / or, in the mixed solution, the concentration of the silver nanowires is 10 mg / L to 100 mg / L, and the concentration of the hydroxypropyl methylcellulose is 1 mg / L to 10 mg / mL; And / or, the solvent is at least one of deionized water, ethanol, and isopropanol.

10. A camouflage device, characterized in that: The invention comprises the patterned electrothermal material according to any one of claims 1 to 3.

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