Temperature-sensitive color-changing ceramic plate and preparation method thereof

Abstract

The invention relates to a temperature-sensitive color-changing ceramic plate and a preparation method thereof. The preparation method of the temperature-sensitive color-changing ceramic plate comprises the following steps: mixing color-changing ink with a diluent, conventionally stirring to uniformly disperse the ink, then adding a suspending agent, a stabilizer and a curing agent, and stirring at a high speed to obtain color-changing ink; pretreating the ceramic tile surface, printing a pattern on the tile surface by using color-changing ink, and performing curing treatment; polishing and grinding the silica sol solution by adopting a high-speed rotating grinding disc so as to form a compact glass protection layer on the surface of the ceramic plate printed with the color-changing patterns; and installing a heating sheet and a power line on the back surface of the ceramic plate to obtain the temperature-sensitive color-changing ceramic plate.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic cold processing, and in particular relates to a temperature-sensitive color-changing ceramic plate and a preparation method thereof. Background Art

[0002] Ceramic panels (ceramic tiles, rock panels) are widely used in indoor and outdoor floor and wall decoration due to their excellent decorative effects and advantages such as ultra-durability, easy cleaning and easy maintenance. The surface decoration effect of traditional ceramic panels is mainly achieved by combining colors, lines, patterns, touch and other processes. After being fired in a kiln at high temperature, the pattern texture is stable, durable and has a good decorative effect. However, the surface decoration effect of traditional ceramic panels is single and belongs to a static decorative effect. That is, after choosing a panel for paving, the surface color, pattern and lines of the panel are fixed and cannot be changed on the panel.

[0003] Color change is a very common phenomenon in nature. Inspired by the color change phenomenon in nature, people have invented a variety of color-changing materials, including thermotropic materials, phototropic materials, electrotropic materials, piezotropic materials, hygrotropic materials, etc. These materials are widely used in the fields of construction, industry, military, anti-counterfeiting, transportation, clothing, etc. If color-changing materials are applied to the field of ceramic plates, it may solve the problem of single ceramic decorative effect. However, the temperature resistance of reversible color-changing materials is usually below 250°C, and they cannot be used in the ceramic sintering process. At the same time, if they are directly printed on the surface of ceramic tiles, the durability of the pattern will become a problem. Summary of the invention

[0004] In view of the above-mentioned technical difficulties, the present invention aims to utilize the unique effects of color-changing materials and provide a temperature-sensitive color-changing ceramic plate and a preparation method thereof. The color-changing ink is modulated into inkjet printing ink, and a color-changing pattern is made on the surface of the ceramic plate by inkjet printing. The color-changing pattern is covered and protected by a firing-free sealing process. While achieving reversible color change, the pattern has good durability, thereby enriching the decorative function of the ceramic plate.

[0005] In a first aspect, the present invention provides a method for preparing a temperature-sensitive color-changing ceramic plate, comprising: The color-changing ink is mixed with a diluent and stirred conventionally to make the ink dispersed evenly, and then a suspending agent, a stabilizer and a curing agent are added and stirred at high speed to obtain the color-changing ink; The ceramic tile surface is pre-treated, and then the pattern is printed on the tile surface with color-changing ink and cured; A high-speed rotating grinding disc is used to polish the silica sol solution to form a dense glass protective layer on the surface of the ceramic plate printed with the color-changing pattern; A heating sheet and a power line are installed on the back of the ceramic plate to obtain the temperature-sensitive color-changing ceramic plate.

[0006] Preferably, the color-changing ink is at least one of a thermochromic ink, a thermochromic / photochromic composite ink, a thermochromic / electrochromic composite ink, or a thermochromic / photochromic / electrochromic composite ink.

[0007] Preferably, the diluent is at least one of oil water, petroleum ether, benzene, xylene or butyl acetate; the suspending agent is at least one of acrylic acid and its modified emulsion, polyurethane emulsion and its modified emulsion or polyethylene glycol emulsion; the stabilizer is at least one of kasone, potassium sorbate or propyl paraben; the curing agent is at least one of isocyanate or epoxyamine; The added amount of the diluent is 5-30% of the mass of the color-changing ink; the added amount of the suspension is 2-5% of the mass of the color-changing ink; the added amount of the stabilizer is 0.5-3% of the mass of the color-changing ink; and the added amount of the curing agent is 0.2-1% of the mass of the color-changing ink.

[0008] Preferably, the conventional stirring speed is 100-300 r / min, and the stirring time is 5-30 min; the high-speed stirring speed is not less than 2000 r / min, and the stirring time is 30-60 min.

[0009] Preferably, the density of the color-changing ink is 1.1 to 1.71 g / cm 3 , viscosity is 12~20mPa·s.

[0010] Preferably, the pretreatment method is polishing or plasma activation treatment, preferably rough polishing, medium polishing and fine polishing are used and the glossiness of the brick surface after fine polishing is controlled to be 30-50°; the printing method of the brick surface pattern is at least one of inkjet printing, screen printing or pad printing, and the mesh size of the screen printing is preferably 200 mesh.

[0011] Preferably, the curing treatment method is at least one of electron beam curing, ultraviolet light curing or heat curing; wherein the voltage of electron beam curing is 100-120 KeV, the current is 5-8 mA, and the curing time is 1-5 seconds; the power of ultraviolet lamp used for ultraviolet light curing is 10000-15000 mW / cm 2 The curing time is 30 to 90 seconds; the heating curing temperature is 80 to 150°C, and the curing time is 2 to 15 minutes.

[0012] Preferably, the polishing speed of the grinding disc is 10000-20000 r / min, and the polishing time is 30-90 s; the grinding disc material is at least one of nylon, foam, wool felt or fiber grinding disc, preferably 5-10 groups of nylon discs, 5-10 groups of foam soft discs, 5-10 groups of wool felt soft discs, and 5-10 groups of fiber discs.

[0013] Preferably, the silica sol solution is one of acidic, neutral or alkaline silica sol solutions, with a solid content of 6-30%, and a usage amount of 30-100 g / m 2 .

[0014] In a second aspect, the present invention provides a temperature-sensitive color-changing ceramic plate obtained according to the above-mentioned preparation method.

[0015] Beneficial Effects (1) The present invention uses color-changing ink as the basis to prepare color-changing ink. After printing, curing, capping and other processes, the brick surface or brick surface pattern can achieve the effect or function of color development, color change or fading under the condition of the presence of a stimulus source. At the same time, the base color, firing pattern and color-changing pattern on the surface of the ceramic plate can be combined to achieve the effect of transforming the static decorative function of the surface of the traditional architectural ceramic plate into a dynamic and static combined decorative function; (2) The present invention can flexibly select color-changing inks with different functions and different color-changing conditions, realize reversible color change, multi-level color change, and indicating color change on the surface or pattern of the ceramic plate, and greatly enrich the decorative function of the ceramic plate. The printed pattern can not only select lines, patterns, textures, etc., but also select QR codes, LOGOs, etc., and can simultaneously realize the decorative function, anti-counterfeiting function or indicating function of the ceramic plate; (3) The present invention adopts a post-processing non-fired capping process, which utilizes silica sol to generate high-temperature dehydration under the action of a high-speed rotating grinding disc, and forms a stable Si-O-Si chemical bond with the silicon dioxide on the surface of the ceramic plate, and finally forms a dense glass protective layer. The protective layer has high hardness, transparency, and light transmittance, good wear resistance, acid and alkali resistance, and pollution resistance, and has uniform thickness, and does not affect the decorative effect and functional effect of the color-changing pattern. At the same time, the process can be applied to other plate fields, such as marble plates, cement plates, soft porcelain materials, terrazzo plates, etc.; (4) The temperature-sensitive color-changing ceramic plate prepared by the present invention has a reversible, multi-level color-changing function. It starts to change color when the color-changing temperature line is reached, and immediately returns to the original color after the temperature is lowered. There can be multiple color-changing temperature lines to display different colors at different temperatures. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The front image of the temperature-sensitive color-changing ceramic plate prepared in Example 1 of the present invention before and after color change; Figure 2 The front image of the temperature-sensitive color-changing ceramic plate prepared in Example 2 of the present invention before and after color change; Figure 3 The front image of the temperature-sensitive color-changing ceramic plate prepared in Example 3 of the present invention before and after color change; Figure 4 This is the back image of the temperature-sensitive color-changing ceramic plate prepared in Example 1 of the present invention; Figure 5 This is the back image of the temperature-sensitive color-changing ceramic plate prepared in Example 2 of the present invention; Figure 6 This is the back image of the temperature-sensitive color-changing ceramic plate prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0017] The present invention is further described below by way of embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, but not to limit the present invention. Unless otherwise specified, each percentage content refers to the percentage content by mass.

[0018] The following is an exemplary description of the preparation method of the temperature-sensitive color-changing ceramic plate provided by the present invention. The preparation method may include the following steps.

[0019] The color-changing ink is prepared by mixing the color-changing ink with a diluent and stirring them conventionally to make the ink fully and evenly dispersed; then a suspending agent, a stabilizer and a curing agent are added and stirred at high speed to obtain the color-changing ink.

[0020] Color-changing inks are usually composed of ink components and color-changing material components. The suspension and stability of the entire system have reached an optimal and balanced state. After dilution, the chemical bonds between the ink components and the color-changing material components will be destroyed, breaking the balance of the original system. Therefore, it is necessary to add suspending agents and stabilizers for directional repair and re-establish the balance between the two. If the stabilizer and suspending agent are added first and then the diluent is added, the stabilizer and suspending agent will first react with the active functional groups on the surface of the original color-changing ink stabilization system. After the diluent is added, directional repair cannot be achieved, and ultimately the stability and suspension of the system cannot be affected. Regarding the curing agent, the curing agent can accelerate the shrinkage rate of the molecular chain of the ink system and achieve accelerated curing. If the curing agent is added before the diluent, the curing agent will first react with the ink system to promote the cross-linking reaction. Adding the diluent will greatly affect the dilution effect.

[0021] In some embodiments, the color-changing ink can be at least one of a thermochromic ink, a thermochromic / photochromic composite ink, a thermochromic / electrochromic composite ink, or a thermochromic / photochromic / electrochromic composite ink; preferably at least one of a reversible thermochromic ink and a composite ink containing a thermochromic ink.

[0022] Among them, the color change temperature of the color-changing ink can be -5 to 73°C, and the color change can be a transition between different colors or a transition between colored and colorless; preferably, green changes to blue and yellow, purple changes to red and blue, blue changes to yellow, green and pink, red changes to yellow, orange changes to yellow, black changes to red, blue and yellow, bright red, pink, rose red, vermilion, orange, yellow, sky blue, dark blue, water blue, grass green, green and black change to colorless.

[0023] In some embodiments, the diluent may be at least one of boiled oil water, petroleum ether, benzene, xylene or butyl acetate; the suspending agent may be at least one of acrylic acid and its modified emulsion, polyurethane emulsion and its modified emulsion or polyethylene glycol emulsion, preferably silicone acrylic emulsion and styrene acrylic emulsion; the stabilizer may be at least one of kasson, potassium sorbate or propyl paraben; the curing agent may be at least one of isocyanate or epoxyamine.

[0024] In some embodiments, the added amount of the diluent can be 5-30% of the mass of the color-changing ink; the added amount of the suspension can be 2-5% of the mass of the color-changing ink; the added amount of the stabilizer can be 0.5-3% of the mass of the color-changing ink; and the added amount of the curing agent can be 0.2-1% of the mass of the color-changing ink.

[0025] Among them, if the mass proportion of the diluent is less than 5%, it will result in the inability to open the chemical bond between the ink component and the color-changing material. If it is higher than 30%, the chemical bond between the ink and the color-changing material will be completely destroyed, resulting in the inability to repair the suspending agent and stabilizer. The content of the suspending agent and stabilizer can be added according to the dilution ratio. The dosage range of the curing agent is usually around 0.5%, not exceeding 1%, which can significantly increase the curing speed of the entire system. Excessive dosage cannot further accelerate the curing speed.

[0026] In some embodiments, the conventional stirring speed may be 100 to 300 r / min, and the stirring time may be 5 to 30 min; the high-speed stirring speed may be controlled to be no less than 2000 r / min, and the stirring time may be 30 to 60 min.

[0027] In some embodiments, the density of the color-changing ink may be 1.1 to 1.71 g / cm 3 , the viscosity can be 12 to 20 mPa·s.

[0028] Pattern printing and curing: The ceramic tile surface is pre-treated, and then the color-changing ink is used to print the tile surface pattern, and then the printed pattern is cured.

[0029] The pretreatment can promote the construction of the microstructure of the ceramic plate and the improvement of the surface activity. In some embodiments, the pretreatment can be polishing or plasma activation, preferably rough polishing, medium polishing, and fine polishing, and the gloss of the brick surface after fine polishing is controlled to be 30 to 50°. The gloss of the brick surface after polishing can directly reflect the roughness and quality of the brick surface. Controlling the gloss of the brick surface after fine polishing within the above range can ensure that the brick surface has a suitable micro-nano structure, and at the same time, the brick surface quality is good and there is no grinding mark.

[0030] The brick surface pattern can be printed by at least one of inkjet printing, screen printing or pad printing, wherein the mesh number of the screen printing can be 200 meshes.

[0031] In some embodiments, the curing treatment method can be at least one of electron beam curing, ultraviolet (UV) curing or heat curing. The voltage of electron beam curing can be 100-120 KeV, the current can be 5-8 mA, and the curing time can be 1-5 seconds; the power of the ultraviolet lamp used for UV curing can be 10000-15000 mW / cm 2 The curing time can be 30 to 90 seconds; the heating curing temperature can be 80 to 150°C, and the curing time can be 2 to 15 minutes.

[0032] Pattern non-firing capping treatment. The high-speed rotating grinding disc is used to polish the silica sol solution to form a dense glass protective layer on the surface of the ceramic plate printed with the color-changing pattern, thereby capping the color-changing pattern on the entire plate surface.

[0033] In some embodiments, the polishing speed of the grinding disc can be 10000-20000 r / min, and the polishing time can be 30-90 s. Controlling the polishing speed and time within the above range can better match the existing production process, and if the polishing speed and time are not appropriate, the glass protective layer will be too thin or too thick, resulting in poor discoloration and decorative effects on the surface of the ceramic plate.

[0034] The grinding disc material can be at least one of nylon, foam, wool felt or fiber grinding discs, preferably 5-10 groups of nylon discs, 5-10 groups of foam soft discs, 5-10 groups of wool felt soft discs, and 5-10 groups of fiber discs. In the present invention, the material of the grinding disc is preferably medium hardness or soft disc, and no hard abrasives such as corundum are added to the grinding disc. The grinding is mainly performed by the soft material of the grinding disc itself, so that the discolored pattern, texture, line and glaze of the plate are not damaged during the grinding process, and local high temperature is generated to make the silica sol lose water to form a glass preservation layer.

[0035] In some embodiments, the silica sol solution may be one of an acidic, neutral or alkaline silica sol solution, preferably an alkaline silica sol solution; the solid content may be 6 to 30%, preferably 8 to 15%; the usage amount may be 30 to 100 g / m 2 If the solid content of the silica sol is too low, a continuous glass protective layer cannot be formed during the polishing process; if the solid content of the silica sol is too high, the silica sol will precipitate, resulting in uneven thickness of the glass protective layer.

[0036] In some embodiments, the thickness of the glass protection layer can be controlled to be 10 to 50 micrometers.

[0037] Different from the organic protective layer formed in occasions such as thermochromic cup decoration, the present invention adopts a post-processing non-firing capping process, which utilizes silica sol to produce high-temperature dehydration under the action of a high-speed rotating grinding disc, and forms a stable Si-O-Si chemical bond with the silicon dioxide on the surface of the ceramic plate, and finally forms a dense glass protective layer. The protective layer has high hardness, transparency, and light transmittance, good wear resistance, acid and alkali resistance, pollution resistance, fire resistance, stability, uniform thickness, and does not affect the decorative effect and functional effect of the color-changing pattern.

[0038] Heat source installation: A heating sheet and a power cord are installed on the back of the ceramic plate to obtain a temperature-sensitive color-changing ceramic plate.

[0039] In some embodiments, the heating sheet can be at least one of a thermally conductive resin heating type, a resistance wire heating type, a semiconductor heating type, or a graphene heating type; and the adapted voltage of the power line power supply is 12 to 220V.

[0040] The present invention uses color-changing ink as the basis to prepare color-changing ink. After printing, curing, capping and other processes, the brick surface or brick surface pattern can achieve the effect or function of coloring, color changing or fading under the condition of the presence of a stimulus source. At the same time, the base color, firing pattern and color-changing pattern on the surface of the ceramic plate can be combined and designed to achieve the effect of transforming the static decorative function of the surface of the traditional building ceramic plate into a dynamic and static combined decorative function.

[0041] The temperature-sensitive color-changing ceramic plate obtained by the preparation method provided by the present invention has a reversible, multi-level color-changing function, starts to change color when reaching the color-changing temperature line, and immediately returns to the original color after the temperature drops. There can be multiple color-changing temperature lines to achieve different colors at different temperatures.

[0042] In some embodiments, the range of different color change temperature lines can be 25-27°C, 31-33°C, 37-39°C, 44-46°C, 59-61°C, 73-75°C; the reversible color change can be Preferably, the above-mentioned multiple temperature lines and color change effects are combined.

[0043] The following examples are further listed to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0044] Unless otherwise specified, the color-changing ink used in the following examples is a reversible thermochromic ink. The color-changing ink and other raw materials used are available on the market. The reversible thermochromic ink stock solution used in the present invention was purchased from Shenzhen Dongfang Bianse Technology Co., Ltd.

[0045] Example 1

[0046] The preparation method of the temperature-sensitive color-changing ceramic plate is as follows: (1) Preparation of color-changing ink. Take a reversible thermochromic ink (the ink color change temperature is 33°C, and the color changes from blue to pink), add a diluent (the mass ratio of oil water: benzene is 3:1, and the mass of the color-changing ink is 30%), and then stir at 100 r / min for 10 minutes, and then continue to add a suspending agent (silicone acrylic emulsion, the mass of the color-changing ink is 5%), a stabilizer (propyl paraben, the mass of the color-changing ink is 3%), and a curing agent (isocyanate, the mass of the color-changing ink is 0.5%), and stir at 2000 r / min for 30 minutes to obtain the color-changing ink (density 1.21 g / cm 3 , viscosity 12.3 mPa·s). (2) Pattern printing and curing. Take a 900mm*1800mm ceramic rock plate after it leaves the kiln, and perform rough polishing, medium polishing, and fine polishing on it. The glossiness of the brick surface after fine polishing is controlled to be 30-50°. Then use an inkjet printer to print the pattern, and use heating to cure the pattern. The curing temperature is 80℃ and the curing time is 3 minutes. (3) Pattern non-burning capping treatment. Use 5 sets of foam soft disks and 10 sets of wool felt soft disks, at a grinding disc speed of 10000r / min, an alkaline silica sol solution solid content of 6%, and a silica sol dosage of 100g / m 2 After polishing for 90 seconds under the conditions of , a dense glass protective layer with a thickness of 10 microns is formed on the surface of the rock plate. (4) Heat source installation: A graphene heating module and a power supply circuit are installed on the back of the ceramic plate to produce a temperature-sensitive color-changing ceramic plate product.

[0047] Figure 1This is a front view image of the temperature-sensitive color-changing ceramic plate prepared in Example 1 of the present invention before and after color change. Figure 4 This is an image of the back of the temperature-sensitive color-changing ceramic plate obtained in Example 1 of the present invention. As can be seen from the figure, when the power is turned on, the graphene heating module starts to heat up, and transfers the heat to the ceramic plate stably and evenly, and the overall temperature of the ceramic plate rises. When the surface temperature of the ceramic plate reaches 33°C or above, the QR code and LOGO pattern printed on the surface of the plate changes from blue to pink.

[0048] Example 2

[0049] The preparation method of the temperature-sensitive color-changing ceramic plate is as follows: (1) Preparation of color-changing ink. Take a reversible thermochromic ink (the ink color change temperature is 38°C, and the color changes from green to yellow), add a diluent (butyl acetate, 5% by mass of the color-changing ink), and then stir at 100 r / min for 10 minutes. Then, add a suspending agent (polyurethane emulsion, 2% by mass of the color-changing ink), a stabilizer (potassium sorbate, 0.5% by mass of the color-changing ink), and a curing agent (isocyanate, 1% by mass of the color-changing ink), and stir at 5000 r / min for 60 minutes to obtain the color-changing ink (density 1.71 g / cm 3 , viscosity 18.3 mPa·s). (2) Pattern printing and curing. Take a 900mm*1800mm ceramic rock plate out of the kiln, and perform rough polishing, medium polishing, and fine polishing on it. Control the glossiness of the brick surface after fine polishing to 30-50°, then use a 200-mesh screen to print the pattern, and use heating to cure the pattern. The curing temperature is 150°C and the curing time is 15 minutes. (3) Pattern non-burning capping treatment. Use 5 sets of foam soft disks, 5 sets of fiber disks, and 6 sets of wool felt soft disks. The grinding disc speed is 20000r / min, the solid content of alkaline silica sol solution is 30%, and the amount of silica sol is 30g / m 2 After polishing for 30 seconds under the conditions of , a dense glass protective layer with a thickness of 45 microns is formed on the surface of the rock plate. (4) Heat source installation: A resistance wire heating module and a power supply circuit are installed on the back of the ceramic plate to obtain a temperature-sensitive color-changing ceramic plate product.

[0050] Figure 2 This is a front view image of the temperature-sensitive color-changing ceramic plate prepared in Example 2 of the present invention before and after color change. Figure 5 This is an image of the back of the temperature-sensitive color-changing ceramic plate obtained in Example 2 of the present invention. As can be seen from the figure, when the power is turned on, the resistance wire heating module starts to heat up, and transfers the heat to the ceramic plate quickly, stably and evenly, and the overall temperature of the ceramic plate rises. When the surface temperature of the ceramic plate reaches 38°C or above, the QR code and LOGO pattern printed on the surface of the plate changes from green to yellow.

[0051] Example 3

[0052] The preparation method of the temperature-sensitive color-changing ceramic plate is as follows: (1) Preparation of color-changing ink. Take a reversible thermochromic ink (the ink color change temperature is 73°C, and the color changes from blue to pink), add a diluent (the mass ratio of petroleum ether: xylene is 2:1, and the mass of the color-changing ink is 15%), and then stir at 300 r / min for 30 minutes, and then continue to add a suspending agent (styrene acrylic emulsion, the mass of the color-changing ink is 5%), a stabilizer (kathion, the mass of the color-changing ink is 1%), and a curing agent (isocyanate, the mass of the color-changing ink is 0.5%), and stir at 5000 r / min for 40 minutes to obtain the color-changing ink (density 1.39 g / cm 3 , viscosity 14.3 mPa·s). (2) Pattern printing and curing. Take a 900mm*1800mm ceramic rock plate out of the kiln, and perform rough polishing, medium polishing, and fine polishing on it. Control the glossiness of the brick surface after fine polishing to 30-50°, then use a 200-mesh screen to print the pattern, and use heating to cure the pattern. The curing temperature is 100°C and the curing time is 5 minutes. (3) Pattern non-burning capping treatment. Use 5 sets of fiber discs and 10 sets of wool felt soft discs. When the grinding disc speed is 12000r / min, the solid content of alkaline silica sol solution is 15%, and the amount of silica sol is 50g / m 2 After polishing for 45 seconds under the conditions of , a dense glass protective layer with a thickness of 25 microns is formed on the surface of the rock plate. (4) Heat source installation: A semiconductor heating module and a power supply circuit are installed on the back of the ceramic plate to produce a temperature-sensitive color-changing ceramic plate product.

[0053] Figure 3 This is the front image of the temperature-sensitive color-changing ceramic plate prepared in Example 3 of the present invention before and after color change. Figure 6 This is an image of the back of the temperature-sensitive color-changing ceramic plate obtained in Example 3 of the present invention. As can be seen from the figure, when the power is turned on, the semiconductor heating module starts to heat up, and transfers the heat to the ceramic plate stably and evenly, and the overall temperature of the ceramic plate rises. When the surface temperature of the ceramic plate reaches 73°C or above, the QR code and LOGO pattern printed on the surface of the plate changes from blue to pink.

[0054] The performance of the prepared thermochromic ceramic plate was tested as follows: (1) The gloss of the ceramic plate was tested using a WGG60-Y4 gloss meter with a test scale of 0.1 GU; (2) The antifouling performance of the ceramic product was tested in accordance with the national standard GB / T 3810.14-2016 Ceramic Tile Test Method Part 14: Determination of Pollution Resistance. The antifouling performance of the treated brick surface was tested. The test process was to bring the test solution and material (pollutant) into contact with the front of the brick for a certain period of time, then clean the brick surface according to the prescribed cleaning method, and observe the visible changes on the brick surface to determine the brick's pollution resistance; (3) The corrosion resistance of the ceramic plate was tested in accordance with GB / T 3810.13-2016 Determination of chemical corrosion resistance, test items include resistance to household liquids, chemical reagents and swimming pool salts (ammonium chloride solution 100g / L, sodium hypochlorite solution 20mg / L) and resistance to low concentration (3% hydrochloric acid solution, citric acid solution 100g / L and potassium hydroxide solution 30g / L) and high concentration acid and alkali (18% hydrochloric acid solution, 5% lactic acid solution and potassium hydroxide solution 100g / L). The results are shown in Tables 1 and 2 below. Table 1 Chemical corrosion resistance test results Example Resistant to household, chemical and swimming pool salts Resistance to low concentration of acid and alkali High concentration acid and alkali resistance 1 GA / GA GLB / GLA / GLB CHB / CHA / CHB 2 GA / GA GLB / GLA / GLB CHB / CHA / CHB 3 GA / GA GLB / GLA / GLA CHB / CHA / CHB Table 2 Test results of pollution resistance and surface gloss Example Antifouling grade Glossiness 1 Chrome green / iodine / olive oil level 5 95.5 2 Chrome green / iodine / olive oil level 5 96 3 Chrome green / iodine / olive oil level 5 94.5 .

[0055] It can be seen that the color-changing ceramic plate prepared by the present invention has good pollution resistance and chemical corrosion resistance, and the anti-fouling level reaches level 5. In addition, the color-changing pattern is protected by a dense glass layer and has good durability and stability.

[0056] Comparative Example 1

[0057] The preparation process of this comparative example refers to that of Example 1, with the main difference being that the glossiness of the ceramic plate after rough polishing, medium polishing and fine polishing is 20 degrees or 60 degrees.

[0058] The gloss of the brick surface after pretreatment in this comparative example is too low or too high. If the gloss is too low, the glass layer on the surface of the prepared thermochromic ceramic material will be too thin, the gloss of the brick surface will be uneven, the anti-fouling grade will be reduced (chrome green level 4 / iodine level 4 / olive oil level 5), and the chemical corrosion resistance will be reduced (high concentration acidity and alkalinity). If the gloss is too high, the prepared thermochromic ceramic material will have the defects of insufficient adhesion of the surface color-changing pattern and the pattern being worn and chipped.

[0059] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A method for preparing a temperature-sensitive color-changing ceramic plate, characterized in that: include: The color-changing ink is mixed with a diluent and stirred conventionally to make the ink dispersed evenly, and then a suspending agent, a stabilizer and a curing agent are added and stirred at high speed to obtain the color-changing ink; Pre-treat the ceramic tile surface, then use color-changing ink to print patterns on the tile surface and perform curing treatment; A high-speed rotating grinding disc is used to polish the silica sol solution to form a dense glass protective layer on the surface of the ceramic plate printed with the color-changing pattern; A heating sheet and a power line are installed on the back of the ceramic plate to obtain the temperature-sensitive color-changing ceramic plate.

2. The preparation method according to claim 1, characterized in that: The color-changing ink is at least one of a thermochromic ink, a thermochromic / photochromic composite ink, a thermochromic / electrochromic composite ink, or a thermochromic / photochromic / electrochromic composite ink.

3. The preparation method according to claim 1 or 2, characterized in that: The diluent is at least one of oil water, petroleum ether, benzene, xylene or butyl acetate; the suspending agent is at least one of acrylic acid and its modified emulsion, polyurethane emulsion and its modified emulsion or polyethylene glycol emulsion; the stabilizer is at least one of kasone, potassium sorbate or propyl paraben; the curing agent is at least one of isocyanate or epoxyamine; The added amount of the diluent is 5-30% of the mass of the color-changing ink; the added amount of the suspension is 2-5% of the mass of the color-changing ink; the added amount of the stabilizer is 0.5-3% of the mass of the color-changing ink; and the added amount of the curing agent is 0.2-1% of the mass of the color-changing ink.

4. The preparation method according to any one of claims 1 to 3, characterized in that The rotation speed of the conventional stirring is 100-300 r / min, and the stirring time is 5-30 min; the speed of the high-speed stirring is not less than 2000 r / min, and the stirring time is 30-60 min.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The density of the color-changing ink is 1.1 to 1.71 g / cm 3 , viscosity is 12~20mPa·s.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The pretreatment method is polishing or plasma activation treatment, preferably rough polishing, medium polishing and fine polishing, and the glossiness of the brick surface after fine polishing is controlled to be 30-50°; the printing method of the brick surface pattern is at least one of inkjet printing, screen printing or pad printing, and the mesh size of the screen printing is preferably 200 meshes.

7. The preparation method according to any one of claims 1 to 6, characterized in that The curing treatment method is at least one of electron beam curing, ultraviolet light curing or heat curing; wherein the voltage of electron beam curing is 100-120 KeV, the current is 5-8 mA, and the curing time is 1-5 seconds; the power of ultraviolet lamp used for ultraviolet light curing is 10000-15000 mW / cm 2 The curing time is 30 to 90 seconds; the heating curing temperature is 80 to 150°C, and the curing time is 2 to 15 minutes.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The polishing speed of the grinding disc is 10000-20000 r / min, and the polishing time is 30-90 s; the grinding disc material is at least one of nylon, foam, wool felt or fiber grinding disc, preferably 5-10 groups of nylon discs, 5-10 groups of foam soft discs, 5-10 groups of wool felt soft discs, and 5-10 groups of fiber discs.

9. The preparation method according to any one of claims 1 to 8, characterized in that: The silica sol solution is one of acidic, neutral or alkaline silica sol solutions, with a solid content of 6-30% and a usage amount of 30-100 g / m 2 .

10. A temperature-sensitive color-changing ceramic plate obtained by the preparation method according to any one of claims 1 to 9.

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