Luminous building coating and preparation method thereof

Abstract

According to the light-emitting building coating and the preparation method thereof, a sol electrophoretic deposition method is adopted for preparing a long-afterglow material, and the obtained light-emitting coating has long afterglow time and high afterglow brightness mainly by improving an electrolyte system in the electrophoretic deposition process and assisting in hydrothermal purification of the performance of the long-afterglow material; the synthesis method is simple in process, good in purification effect and suitable for the fields of roads, walls, lighting buildings, anti-counterfeiting marks and the like.

Description

Technical Field

[0001] The present invention relates to a luminous architectural coating and a preparation method thereof, and in particular to a luminous coating prepared by combining a high-performance long afterglow material with a water-based coating and a preparation method thereof, which is suitable for the fields of roads, walls, lighting buildings, anti-counterfeiting labels and the like. Background Art

[0002] Green luminous paint is also called photoluminescent paint. It is a kind of light functional paint, which is different from other light functional paints such as fluorescent paint, reflective paint, self-luminous paint, etc. The substance that can emit light is long afterglow luminescent powder. Long afterglow luminescent powder refers to a photoluminescent material that can absorb and store the energy of external light radiation under the irradiation of natural light or other artificial light sources, and then slowly release the stored energy in the form of visible light under any room temperature conditions for a considerable period of time. In the long process of production practice and social practice, people have found some pure natural minerals that can continue to glow in the dark after being exposed to sunlight for a period of time. Its characteristic is that after absorbing various visible light sources such as sunlight, lamplight, external stray light, etc., it will automatically and continuously emit light in the dark, giving people more indication information. It does not require power supply, and it also has the characteristics of non-radioactivity, non-toxicity, non-pollution, and stable chemical properties.

[0003] In recent years, the methods for preparing photoluminescent materials have been continuously developed, and there are many methods, mainly including the impregnation-pulling method for preparing single crystals and the solid-phase reaction method for preparing polycrystalline powders, hydrothermal synthesis method, sol-gel method, combustion method, precipitation method, molten salt method, etc. The solid-phase reaction method generally obtains the product by calcination at high temperature; the hydrothermal synthesis method requires a reaction under high pressure to obtain the product; the sol-gel method is a method in which a sol is first prepared and then gelled, and then calcined at a certain temperature to remove organic matter to obtain the product; the combustion method is a process in which nitrate is used as an oxidant and urea as a reducing agent, and the product is obtained after the reaction is completed in a short time; the precipitation method is a method in which a precipitate containing the ions required for the product is first prepared, and then the precipitate is placed under certain conditions and calcined to obtain the product; the molten salt method is a method in which the reactants are mixed with low-melting-point salts and then the powder is synthesized at a relatively low temperature.

[0004] Among them, the sol-gel method originated in 1846 when French chemist JJ Ebelmen mixed SiCl4 with ethanol and found that it hydrolyzed in wet air and formed a gel. Sol is a colloidal system with liquid characteristics, and the dispersed particles are solids or macromolecules between 1 and 1000nm; Gel is a colloidal system with solid characteristics, and the dispersed substances form a continuous network skeleton, and the skeleton gaps are filled with liquid or gas. The content of the dispersed phase in the gel is very low, generally between 1% and 3%.

[0005] The sol-gel method is to dissolve inorganic salts containing highly chemically active components and metal alkoxides or other organic salts in water or organic solvents to form a uniform solution. The solute and the solvent undergo hydrolysis, alcoholysis or integration reactions. The reaction products aggregate into ions of about 1 nm and form a sol. The sol is evaporated and dried to form a gel. The gel is dried and heat treated to obtain the product. For example, the sol-gel method was used to successfully prepare Sr2MgSi2O7: Eu 2+ ,Dy 3+ The process can be divided into the following steps: 1. After Sr(NO3)2, Eu(NO3)3, Dy(NO3)3, and Mg(NO3)2 are dissolved in deionized water, a certain amount of acetic acid is added; an appropriate amount of deionized water and ethanol are added to Si(OC2H5)4. 2. The above solutions are slowly mixed and stirred evenly, and a gel is obtained in a 50°C water bath, and then the gel is placed in a 90°C oven for drying for 12 hours. 3. The dried gel powder is evenly ground in an agate mortar and calcined in a reducing atmosphere at 1000~1200°C to obtain the product.

[0006] In addition, the prior art includes the preparation of long afterglow materials by electrochemical methods, such as CN104746125A, an electrochemical assembly method of a titanate afterglow particle ZMS-5 composite material, with a long afterglow luminescent guest Zn 0.2 Ca 0.8 TiO3:Pr 3+ The Zn was successfully synthesized by using the cathode electrophoresis deposition method with the sol as the electrophoresis solution and ZMS-5 as the working electrode. 0.2 Ca 0.8 TiO3:Pr 3+ ZMS-5 composite material, the method adopted in this patent is sol electrophoretic deposition, which is to disperse solid nanobeams or ions in the sol to form surface charges, and rely on the electrostatic double layer formed by the surrounding ions with opposite charges to maintain stability. When an external electric field is introduced into the system, the charged nanobeams or particles will move in a directed manner and be deposited in a molecular sieve with a certain shape after simple encapsulation to complete the assembly.

[0007] CN111234806B aims to solve the defect in the prior art that the sol-gel silica coating layer of the aluminate long afterglow material is easy to crack during the gelation or drying process and eventually cannot be used. The invention provides a method for preparing a silica coating layer which can improve the film yield of the silica coating layer in the gel drying process, wherein the method for preparing the aluminate long afterglow material comprises: 1. weighing ethyl orthosilicate, anhydrous ethanol and deionized water according to the mass proportion, and mixing them thoroughly; 2. heating the mixed solution to above 50°C, adjusting the solution to alkalinity with sodium hydroxide, and continuing the reaction for 30 minutes; 3. raising the temperature of the mixed solution to above 70°C, and continuing the reaction until the mixed solution changes from transparent to milky white and the Tyndall effect appears; 4. adding the aluminate long afterglow material therein, stirring and dispersing it; 5. sealing the stirred and dispersed long afterglow material mixture, and aging it at room temperature for more than 2 hours; 6. placing the aged material in a high and low temperature alternating wet heat box, and heat treating it for more than 1 hour under the conditions of 60-90°C and 60%-90% RH humidity, with a heating rate of 1°C / min; 7. taking out the treated material, and drying it at room temperature to obtain the silica-coated long afterglow material. Summary of the invention

[0008] The present invention prepares a luminescent building coating and a preparation method thereof, and also adopts the sol electrophoretic deposition method to prepare the long afterglow material. The electrolyte system in the electrophoretic deposition process is improved, and the performance of the long afterglow material is assisted by hydrothermal purification. The obtained luminescent coating has a longer afterglow time and higher afterglow brightness, and is suitable for the fields of roads, walls, lighting buildings, anti-counterfeiting labels, etc. The preparation process has the advantages of easy control, high efficiency, low cost, easy operation, etc.

[0009] Specifically: A method for preparing a luminous architectural coating comprises the following steps: (1) Place deionized water, ethylene glycol, Digo 902W defoamer, Nopco SN5040 dispersant, and Digo KL245 wetting agent into a container and stir at 200-300 rpm for 10-15 minutes; (2) At 200-300 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in sequence, and then disperse them at high speed at 2000-3000 rpm for 10-15 minutes, then add the long afterglow luminescent material, and then homogenize at high speed at 2000-3000 rpm for 20-40 minutes; (3) Add silicone acrylic emulsion, BYK-361N leveling agent and thickener under stirring at 400-500 rpm, and continue stirring for 10-30 minutes to obtain the desired luminous architectural coating; The long afterglow luminescent material is prepared by the following steps: (a) Mixing a certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid in 50 mL of deionized water, stirring evenly with a magnetic stirrer, adjusting the pH value with hydrochloric acid, and then adding polyethylene glycol. After continuing to stir evenly, stirring in a water bath at 70-90° C. until a gel state is obtained, thereby obtaining a sol-gel precursor solution. (b) placing the sol-gel precursor solution prepared in step (a) in a reactor containing an ionic liquid, mixing them thoroughly under inert gas and magnetic stirring conditions, inserting an inert metal sheet electrode into the reactor, and then sealing the reactor, turning on the power supply to perform constant potential electrochemical treatment, and then starting a programmed temperature heating reactor, wherein the programmed temperature heating parameter is 4-5°C / min to 70-80°C and then maintaining the temperature for 30-40min, then turning off the power supply, continuing to heat the reactor at 4-5°C / min to 100-102°C and then maintaining the temperature for 5-10min, and then naturally cooling to room temperature, taking out the cathode electrode, scraping off the deposits on the surface of the cathode electrode, washing and drying to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent material.

[0010] The ionic liquid is selected from 1-butanesulfonic acid-3-methylimidazolium hydrogen sulfate or 1-ethyl-3-methylimidazolium hydrogen sulfate.

[0011] The mass ratio of the sol-gel precursor solution to the ionic liquid is 1:(15-20).

[0012] In certain embodiments, hydrochloric acid is used to adjust the pH to 1-3.

[0013] In certain embodiments, the molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(1.8-2.2):(0.9-1.1), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1-1.5):(1.2-1.3).

[0014] In certain embodiments, the voltage of the constant potential electrochemical treatment is 7-10 V and the time is 10-15 min.

[0015] A luminous architectural coating, wherein the components of the luminous architectural coating include, by weight: 30-40 parts of silicone acrylic emulsion; 5-25 parts of long afterglow luminescent material; 3-5 parts of heavy calcium carbonate; 6-7 parts of light calcium carbonate; Ordinary titanium dioxide 8-10 parts; ethylene glycol, 2-4 parts; BYK-361N leveling agent 0.3-0.4 parts; Thickener 0.4-0.8 parts; 0.3-0.4 parts of high 902W defoamer; Nopco SN5040 dispersant 1.0 -1.5 parts; Digo KL245 wetting agent 0.3-0.4 parts; 30-40 parts of deionized water.

[0016] Beneficial technical effects: The present invention adopts an ionic liquid electrophoresis system for the first time to prepare a long afterglow luminescent material, and the corresponding technical effect is significantly better than that of a deionized water system. By adjusting the hydrothermal and programmed temperature parameters, the formation of the electrophoretic sol and the long afterglow material can be effectively controlled. The obtained long afterglow material has a longer afterglow time and a higher afterglow brightness. When used in water-based coatings, the coating has excellent performance, good storage and stability, and can meet practical application requirements. At the same time, its water resistance and alkali resistance meet the requirements of coating detection standards, and it has good luminescence durability. DETAILED DESCRIPTION Example 1

[0017] A method for preparing a luminous architectural coating comprises the following steps: (1) Place deionized water, ethylene glycol, Digo 902W defoamer, Nopco SN5040 dispersant, and Digo KL245 wetting agent into a container and stir at 200 rpm for 10 min.

[0018] (2) At 200 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in turn, and then disperse them at high speed at 2000 rpm for 10 minutes. Then add the long afterglow luminescent material and homogenize them at 2000 rpm for 20 minutes.

[0019] (3) Then add silicone acrylic emulsion, BYK-361N leveling agent and thickener while stirring at 400 rpm, and continue stirring for 10 minutes to obtain the desired luminous architectural coating.

[0020] The long afterglow luminescent material is prepared by the following steps.

[0021] (a) A certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid are sequentially mixed in 50 mL of deionized water, and after magnetic stirring, the pH value is adjusted to 1 with hydrochloric acid, and then polyethylene glycol is added. After continuing to stir evenly, stirring in a water bath at 70-90° C. until a gel state is obtained to obtain a sol-gel precursor solution; wherein the molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(1.8):(0.9), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1):(1.2).

[0022] (b) placing the sol-gel precursor prepared in step (a) in a reactor containing an ionic liquid, wherein the ionic liquid is selected from 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate, and the mass ratio of the sol-gel precursor to the ionic liquid is 1:(15), and the mixture is fully mixed under inert gas and magnetic stirring conditions. An inert metal sheet electrode is inserted into the reactor, and then the reactor is sealed and the power is turned on to perform a constant potential electrochemical treatment at a voltage of 7 V for 10 min. Then, the reactor is heated by a programmed temperature increase, and the programmed temperature increase parameter is 4°C / min to 70°C and then kept constant for 30 min. Then, the power is turned off and the temperature is continued to be increased at 4°C / min to 100°C and then continued for 5 min. Then, the mixture is naturally cooled to room temperature, the cathode electrode is taken out, the deposit on the surface of the cathode electrode is scraped off, and the mixture is washed and dried to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent materials The components of the luminous architectural coating include: 30 parts of silicone acrylic emulsion, 5 parts of long afterglow luminescent material, 3 parts of heavy calcium carbonate, 6 parts of light calcium carbonate, 8 parts of ordinary titanium dioxide; 2 parts of ethylene glycol, 0.3 parts of BYK-361N leveling agent; 0.4 parts of thickener; 0.3 parts of Digo 902W defoaming agent; 1.0 parts of Nopco SN5040 dispersant; 0.3 parts of Digo KL245 wetting agent; and 30 parts of deionized water. Example 2

[0023] A method for preparing a luminous architectural coating comprises the following steps: (1) Place deionized water, ethylene glycol, Deco 902W defoamer, Nopco SN5040 dispersant, and Deco KL245 wetting agent into a container and stir at 250 rpm for 12.5 min.

[0024] (2) At 250 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in turn, and then disperse them at high speed at 2500 rpm for 12.5 minutes. Then add the long afterglow luminescent material and homogenize them at 2500 rpm for 30 minutes.

[0025] (3) Then add silicone acrylic emulsion, BYK-361N leveling agent and thickener while stirring at 450 rpm, and continue stirring for 20 minutes to obtain the desired luminous architectural coating.

[0026] The long afterglow luminescent material is prepared by the following steps.

[0027] (a) A certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid are sequentially mixed in 50 mL of deionized water, and after magnetic stirring, the pH value is adjusted to 2 with hydrochloric acid, and then polyethylene glycol is added. After continuing to stir evenly, stirring is carried out in a water bath at 80°C until a gel state is obtained to obtain a sol-gel precursor solution; wherein the molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(2):(1), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1.25):(1.25).

[0028] (b) placing the sol-gel precursor prepared in step (a) in a reactor containing an ionic liquid, wherein the ionic liquid is selected from 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate, and the mass ratio of the sol-gel precursor to the ionic liquid is 1:17.5. The mixture is fully mixed under inert gas and magnetic stirring conditions, and an inert metal sheet electrode is inserted into the reactor. The reactor is then sealed and the power is turned on to perform a constant potential electrochemical treatment at a voltage of 8.5 V for 12.5 min. The reactor is then heated by a programmed temperature increase, with the programmed temperature increase parameter being 4.5°C / min to 75°C and then kept at a constant temperature for 35 min. The power is then turned off and the temperature is continued to be increased at 4.5°C / min to 101°C and then continued for 7.5 min. The mixture is then naturally cooled to room temperature, the cathode electrode is removed, the deposit on the surface of the cathode electrode is scraped off, and the mixture is washed and dried to obtain a ZnCa2O4:Mn2O4-based quartz salt. 2+ Long afterglow luminescent material.

[0029] The components of the luminous architectural coating include: 35 parts of silicone acrylic emulsion, 15 parts of long afterglow luminescent material, 4 parts of heavy calcium carbonate, 6.5 parts of light calcium carbonate, 9 parts of ordinary titanium dioxide; 3 parts of ethylene glycol, 0.35 parts of BYK-361N leveling agent; 0.6 parts of thickener; 0.35 parts of Digo 902W defoaming agent; 1.25 parts of Nopco SN5040 dispersant; 0.35 parts of Digo KL245 wetting agent; and 35 parts of deionized water. Example 3

[0030] A method for preparing a luminous architectural coating comprises the following steps: (1) Place deionized water, ethylene glycol, Digo 902W defoamer, Nopco SN5040 dispersant, and Digo KL245 wetting agent into a container and stir at 300 rpm for 15 min.

[0031] (2) At 300 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in turn, and then disperse them at high speed at 3000 rpm for 15 minutes. Then add the long afterglow luminescent material and homogenize them at 3000 rpm for 40 minutes.

[0032] (3) Then add silicone acrylic emulsion, BYK-361N leveling agent and thickener while stirring at 500 rpm, and continue stirring for 30 minutes to obtain the desired luminous architectural coating.

[0033] The long afterglow luminescent material is prepared by the following steps.

[0034] (a) A certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid are sequentially mixed in 50 mL of deionized water, and after magnetic stirring, the pH is adjusted to 3 with hydrochloric acid, and then polyethylene glycol is added. After continuing to stir evenly, stirring is carried out in a water bath at 90°C until a gel state is obtained to obtain a sol-gel precursor solution; wherein the molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(2.2):(1.1), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1.5):(1.3).

[0035] (b) placing the sol-gel precursor prepared in step (a) in a reactor containing an ionic liquid, wherein the ionic liquid is selected from 1-ethyl-3-methylimidazolium hydrogen sulfate, and the mass ratio of the sol-gel precursor to the ionic liquid is 1:(20), and the mixture is fully mixed under inert gas and magnetic stirring conditions. An inert metal sheet electrode is inserted into the reactor, and then the reactor is sealed and the power is turned on to perform a constant potential electrochemical treatment at a voltage of 10 V for 15 min. Then, the reactor is heated by a programmed temperature increase, wherein the temperature is increased by 5°C / min to 80°C and then maintained at a constant temperature for 40 min. Then, the power is turned off and the temperature is continued to be increased by 5°C / min to 102°C and then maintained for 10 min. Then, the reactor is naturally cooled to room temperature, the cathode electrode is removed, the deposit on the surface of the cathode electrode is scraped off, and the reactor is washed and dried to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent material.

[0036] The components of the luminous architectural coating include: 40 parts of silicone acrylic emulsion, 25 parts of long afterglow luminescent material, 5 parts of heavy calcium carbonate, 7 parts of light calcium carbonate, 10 parts of ordinary titanium dioxide; 4 parts of ethylene glycol, 0.4 parts of BYK-361N leveling agent; 0.8 parts of thickener; 0.4 parts of Digo 902W defoaming agent; 1.5 parts of Nopco SN5040 dispersant; 0.4 parts of Digo KL245 wetting agent; and 40 parts of deionized water.

[0037] Comparative Example 1, a method for preparing a luminous architectural coating, comprising the following steps: (1) Place deionized water, ethylene glycol, Deco 902W defoamer, Nopco SN5040 dispersant, and Deco KL245 wetting agent into a container and stir at 250 rpm for 12.5 min.

[0038] (2) At 250 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in turn, and then disperse them at high speed at 2500 rpm for 12.5 minutes. Then add the long afterglow luminescent material and homogenize them at 2500 rpm for 30 minutes.

[0039] (3) Then add silicone acrylic emulsion, BYK-361N leveling agent and thickener while stirring at 450 rpm, and continue stirring for 20 minutes to obtain the desired luminous architectural coating.

[0040] The long afterglow luminescent material is prepared by the following steps.

[0041] (a) A certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid are sequentially mixed in 50 mL of deionized water, and after magnetic stirring, the pH value is adjusted to 2 with hydrochloric acid, and then polyethylene glycol is added. After continuing to stir evenly, stirring is carried out in a water bath at 80°C until a gel state is obtained to obtain a sol-gel precursor solution; wherein the molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(2):(1), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1.25):(1.25).

[0042] (b) placing the sol-gel precursor solution prepared in step (a) in a reactor containing deionized water, and fully mixing it under inert gas and magnetic stirring conditions, inserting an inert metal sheet electrode into the reactor, and then sealing the reactor, turning on the power supply to perform constant potential electrochemical treatment at a voltage of 8.5 V for 12.5 min, and then starting a temperature program to heat the reactor at a temperature program parameter of 4.5°C / min to 75°C and then keeping the temperature constant for 35 min, and then naturally cooling to room temperature, taking out the cathode electrode, scraping off the sediment on the surface of the cathode electrode, washing and drying to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent material.

[0043] The components of the luminous architectural coating include: 35 parts of silicone acrylic emulsion, 15 parts of long afterglow luminescent material, 4 parts of heavy calcium carbonate, 6.5 parts of light calcium carbonate, 9 parts of ordinary titanium dioxide; 3 parts of ethylene glycol, 0.35 parts of BYK-361N leveling agent; 0.6 parts of thickener; 0.35 parts of Digo 902W defoaming agent; 1.25 parts of Nopco SN5040 dispersant; 0.35 parts of Digo KL245 wetting agent; and 35 parts of deionized water.

[0044] Comparative Example 2, a method for preparing a luminous architectural coating, comprising the following steps: (1) Place deionized water, ethylene glycol, Deco 902W defoamer, Nopco SN5040 dispersant, and Deco KL245 wetting agent into a container and stir at 250 rpm for 12.5 min.

[0045] (2) At 250 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in turn, and then disperse them at high speed at 2500 rpm for 12.5 minutes. Then add the long afterglow luminescent material and homogenize them at 2500 rpm for 30 minutes.

[0046] (3) Then add silicone acrylic emulsion, BYK-361N leveling agent and thickener while stirring at 450 rpm, and continue stirring for 20 minutes to obtain the desired luminous architectural coating.

[0047] The long afterglow luminescent material is prepared by the following steps.

[0048] (a) A certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid are sequentially mixed in 50 mL of deionized water, magnetically stirred, adjusted to pH 2 with hydrochloric acid, and then polyethylene glycol is added. The mixture is stirred evenly and then stirred in a water bath at 80° C. until a gel state is obtained to obtain a sol-gel precursor solution. The molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(2):(1), the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1.25):(1.25), the ionic liquid is selected from 1-butylsulfonic acid-3-methylimidazole hydrogen sulfate, and the mass ratio of the sol-gel precursor solution to the ionic liquid is 1:17.5.

[0049] (b) placing the sol-gel precursor prepared in step (a) in a reactor containing an ionic liquid, wherein the ionic liquid is selected from 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate, and the mass ratio of the sol-gel precursor to the ionic liquid is 1:17.5, and the mixture is fully mixed under inert gas and magnetic stirring conditions, an inert metal sheet electrode is inserted into the reactor, and then the reactor is sealed, and the power is turned on to perform constant potential electrochemical treatment at a voltage of 8.5 V for 12.5 min, and then the reactor is heated by a programmed temperature increase at a program temperature increase parameter of 4.5°C / min to 75°C and then kept at a constant temperature for 35 min, and then the power is turned off, and the mixture is naturally cooled to room temperature, the cathode electrode is taken out, the deposit on the surface of the cathode electrode is scraped off, and the mixture is washed and dried to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent material.

[0050] The components of the luminous architectural coating include: 35 parts of silicone acrylic emulsion, 15 parts of long afterglow luminescent material, 4 parts of heavy calcium carbonate, 6.5 parts of light calcium carbonate, 9 parts of ordinary titanium dioxide; 3 parts of ethylene glycol, 0.35 parts of BYK-361N leveling agent; 0.6 parts of thickener; 0.35 parts of Digo 902W defoaming agent; 1.25 parts of Nopco SN5040 dispersant; 0.35 parts of Digo KL245 wetting agent; and 35 parts of deionized water.

[0051] Example 2 Long afterglow material ZnCa2O4:Mn 2+The initial afterglow intensity is 6872mcd / m 2 , afterglow intensity 87mcd / m at 2h 2 After being prepared as a coating, the initial afterglow brightness of the corresponding coating decreased from 6872 mcd / m 2 Reduced to 4827mcd•m-2, a decrease of 30%.

[0052] Comparative Example 1 Long afterglow material ZnCa2O4:Mn 2+ The initial afterglow intensity is 798mcd / m 2 , afterglow intensity 3.8mcd / m at 2h 2 After being prepared as a coating, the initial afterglow brightness of the corresponding coating decreased from 798mcd / m 2 Reduced to 526 mcd / m 2 , a decrease of 34%.

[0053] Comparative Example 2 Long afterglow material ZnCa2O4:Mn 2+ The initial afterglow intensity is 1587mcd / m 2 , afterglow intensity 6.8mcd / m at 2h 2 After being prepared as a coating, the initial afterglow brightness of the corresponding coating decreased from 1587mcd / m 2 Reduced to 1079 mcd / m 2 .

[0054] The afterglow test shows that the long afterglow material prepared by the present invention and the corresponding luminescent coating have a long afterglow time and a high afterglow brightness. The possible reason is that the ionic liquid system used in the present invention is excellent, and the excellent ZnCa2O4:Mn is obtained by electrochemical cathode adsorption gel, hydrothermal treatment, and finally power-off high-temperature hydrothermal treatment. 2+ Material, the afterglow material is blue-green.

[0055] It should be noted that the above specific embodiments are exemplary, and those skilled in the art may come up with various solutions inspired by the disclosure of the present invention, and these solutions also belong to the disclosure scope of the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing a luminous architectural coating, characterized in that The steps include: (1) Place deionized water, ethylene glycol, Digo 902W defoamer, Nopco SN5040 dispersant, and Digo KL245 wetting agent into a container and stir at 200-300 rpm for 10-15 minutes; (2) At 200-300 rpm, add heavy calcium carbonate, light calcium carbonate and titanium dioxide into the container in sequence, and then disperse them at high speed at 2000-3000 rpm for 10-15 minutes, then add the long afterglow luminescent material, and then homogenize at high speed at 2000-3000 rpm for 20-40 minutes; (3) Add silicone acrylic emulsion, BYK-361N leveling agent and thickener under stirring at 400-500 rpm, and continue stirring for 10-30 minutes to obtain the desired luminous architectural coating; The long afterglow luminescent material is prepared by the following steps: (a) Mixing a certain amount of zinc nitrate, calcium nitrate, manganese nitrate and citric acid in 50 mL of deionized water, stirring evenly with a magnetic stirrer, adjusting the pH value with hydrochloric acid, and then adding polyethylene glycol. After continuing to stir evenly, stirring in a water bath at 70-90° C. until a gel state is obtained, thereby obtaining a sol-gel precursor solution. (b) placing the sol-gel precursor solution prepared in step (a) in a reactor containing an ionic liquid, mixing them thoroughly under inert gas and magnetic stirring conditions, inserting an inert metal sheet electrode into the reactor, and then sealing the reactor, turning on the power supply to perform constant potential electrochemical treatment, and then starting a programmed temperature heating reactor, wherein the programmed temperature heating parameter is 4-5°C / min to 70-80°C and then maintaining the temperature for 30-40min, then turning off the power supply, continuing to heat the reactor at 4-5°C / min to 100-102°C and then maintaining the temperature for 5-10min, and then naturally cooling to room temperature, taking out the cathode electrode, scraping off the deposits on the surface of the cathode electrode, washing and drying to obtain a ZnCa2O4:Mn 2+ Long afterglow luminescent material.

2. The method for preparing a luminous architectural coating according to claim 1, characterized in that The ionic liquid is selected from 1-butanesulfonic acid-3-methylimidazolium hydrogen sulfate or 1-ethyl-3-methylimidazolium hydrogen sulfate.

3. The method for preparing a luminous architectural coating according to claim 1, characterized in that The mass ratio of the sol-gel precursor solution to the ionic liquid is 1:(15-20).

4. The method for preparing a luminous architectural coating according to claim 1, characterized in that Use hydrochloric acid to adjust pH to 1-3.

5. The method for preparing a luminous architectural coating according to claim 1, characterized in that The molar ratio of zinc nitrate, calcium nitrate, manganese nitrate and citric acid is 1:(1.8-2.2):(0.9-1.1), and the molar ratio of citric acid, total metal ions and polyethylene glycol is 1:(1-1.5):(1.2-1.3).

6. The method for preparing a luminous architectural coating according to claim 1, characterized in that The voltage of the constant potential electrochemical treatment is 7-10V and the time is 10-15min.

7. A luminous architectural coating obtained by the method for preparing a luminous architectural coating as claimed in any one of claims 1 to 6, characterized in that: The components of the luminous architectural coating include, by weight: 30-40 parts of silicone acrylic emulsion; 5-25 parts of long afterglow luminescent material; 3-5 parts of heavy calcium carbonate; 6-7 parts of light calcium carbonate; 8-10 parts of titanium dioxide; 2-4 parts of ethylene glycol; BYK-361N leveling agent 0.3-0.4 parts; Thickener 0.4-0.8 parts; 0.3-0.4 parts of Degao 902W defoamer; Nopco SN5040 dispersant 1.0 -1.5 parts; Digo KL245 wetting agent 0.3-0.4 parts; 30-40 parts of deionized water.