Building luminescent coating and preparation method thereof

Abstract

According to the building luminescent coating and the preparation method thereof, a local super-alkali state is created through an electro-deposition template method, SrNb2O6: Eu < 3 + > is finally obtained, the SrNb2O6: Eu < 3 + > is a red luminescent material with excellent performance, the luminescent color coordinate is very close to the red standard value, the purity of red is very high, and the SrNb2O6: Eu < 3 + > is a red luminescent material with excellent performance. When being applied to building coatings, the coating has the properties of delayed luminescence, light enhancement and shining, greenness, environmental protection and energy conservation.

Description

Technical Field

[0001] The invention belongs to the field of coatings, and specifically relates to a method for preparing a luminous coating with good comprehensive performance using epoxy resin and polyurethane as base materials. The luminous coating can be used in the field of luminous coatings for building signs and road marking paints on highways, expressways, urban roads, subways, etc. Background Art

[0002] Luminescent paint is composed of luminescent pigment, film-forming material (base resin, inorganic pigment, filler, additives, etc. Luminescent pigment is the main functional component of luminescent paint. Luminescent paint is generally divided into fluorescent paint, self-luminous paint, light-storage luminescent paint, etc.

[0003] Fluorescent paint: Fluorescent paint is a paint that glows when exposed to ultraviolet light. Its characteristic is that it glows when exposed to ultraviolet light and becomes completely dim when the exposure stops. White luminous paint: Self-luminous paint not only contains materials used for light-storing paint, but also uses substances that can generate radiation energy and glow. Its characteristic is that the afterglow of the light varies with the type and amount of trace radioactive substances added. Because it contains radioactive substances that are harmful to the human body, its application is limited. Light-storing luminous paint: Light-storing luminous paint can absorb sunlight or electric light, and can emit light after storing light. Its characteristic is that it has countless repeatability of absorption-luminescence-absorption-luminescence. Its luminous color and luminous time vary with time and the type of phosphor used.

[0004] Features of luminous paint: (1) Long afterglow time. The long afterglow luminous powder is used as the luminous material, and the afterglow time is long, which is far longer than the afterglow time of the traditional sulfide luminous material, which is only less than 30 minutes. Therefore, the paint can save energy when used on interior walls. (2) Good decorative effect. At present, the real estate industry is highly competitive, and the grade of the developed communities is getting higher and higher, and the functions are getting more and more complete. In order to play an advantage in the competition, each community is not only decorated very beautifully during the day, but also needs to be decorated on the surface of the building at night. (3) Energy saving With the development of urban lighting projects, many buildings are covered with decorative lights. When night falls, the lights are all on, which is very beautiful. However, this beautiful night view is obtained by consuming a lot of electricity. "my country is in a stage of rapid economic development. The demand for electricity and energy is huge. In recent years, many areas have experienced power outages due to power shortages. The use of water-based energy storage luminous paint on building exterior walls can replace electric lights. (4) Non-toxic and non-radioactive The paint is a water-based paint made of a preferred polymer emulsion and various additives and auxiliaries. It does not contain volatile toxic solvents, and uses ultra-long afterglow luminous powder as the luminous material. It does not contain radioactive elements. It is a non-toxic, harmless and environmentally friendly product. It is safe to produce and construct, non-flammable, and can be used in any environment. Traditional luminous paints often add radioactive elements to extend the afterglow time, which is harmful to the human body. (5) Long luminous life The luminous process of this paint is a physical process. Its principle is luminescence. When the material is irradiated with visible light wavelength (320-760mm), the atoms of the material absorb light energy, and the electrons outside the nucleus jump from the low energy layer to the high energy layer far from the nucleus. At this time, the atoms are in an excited state. The material is unstable in the excited state, so the electrons in the high energy layer will quickly jump back to the low energy layer and release the energy in the form of light energy. This part of light is the emission light seen in the dark. Therefore, the luminous life of the paint is very long and can last for more than 10 years. (6) The luminous brightness can be adjusted. The luminous brightness of the paint can be adjusted according to the surrounding environment and decoration needs by adjusting the dosage of the luminescent material during production or adjusting the thickness of the paint during construction. (7) Good storage stability. The ultra-long afterglow luminescent powder is coated and treated to be a durable luminescent powder. By selecting the additive and using special production processes and equipment, the paint has good storage stability, overcoming the stratification and precipitation phenomenon that the paint is easy to occur due to the high density of the luminescent powder.

[0005] Functions of coatings: (1) Coatings are used for decoration. Coatings make the world around us, including urban appearance, home environment, and transportation, colorful. (2) Coatings can protect materials and protect them from or reduce damage and corrosion, such as protecting metal materials from sunlight, wind and rain. (3) Coatings can be used for marking, such as preparing traffic road separation lines or various signboards on traffic roads, which can still be clear and bright in the dark. In factories, various pipelines, light buttons, exit signs, etc. can also be found in the dark. (4) Special functions. In addition to the above-mentioned common functions, coatings also have six special functions: mechanical functions, such as wear-resistant coatings and lubricating coatings; thermal functions, such as temperature-indicating coatings, high-temperature-resistant coatings, and fire-retardant coatings; electromagnetic functions, such as conductive coatings and anti-static coatings; optical functions, such as luminous coatings, fluorescent coatings, and reflective coatings; biological functions, such as anti-fouling coatings and mildew-proof coatings; chemical functions, such as acid-resistant and alkali-resistant coatings.

[0006] Regarding luminescent materials, Shaanxi University of Science and Technology has disclosed a europium-doped cubic sodium strontium niobate red luminescent powder and its preparation method: according to the molar ratio of the substances being (0.75-1):1:0.5x, SrCO3, Nb2O5, and Eu2O3 are weighed as raw materials, wherein x=0.01-0.1; the raw materials are ground at room temperature until the raw materials are fully mixed and then used; according to the mass ratio of the total mass of SrCO3 and Nb2O5 to NaCl being 1:(3-9), NaCl is weighed as The method comprises the following steps: preparing a molten salt, mixing the molten salt with a raw material, grinding the mixture at room temperature, and uniformly mixing the raw material with the molten salt to obtain a mixed powder; the europium-doped sodium strontium niobate luminescent powder prepared by the molten salt method has a purity of almost 100%, good crystallization performance, few defects, uniform particle size and good dispersibility, and extremely high red light color purity, which is close to a standard red light point. Compared with other methods, the molten salt method adopted by the present invention has the advantages of simple experimental device, easy operation, controllable particle size, short synthesis cycle, and is suitable for preparing luminescent powder with a particle size of several microns, uniform particle distribution and regular morphology. Summary of the invention

[0007] The present invention provides a building luminous paint and a preparation method thereof, wherein SrNb2O6:Eu 3+ It is a red luminescent material with excellent performance. The color coordinates of the luminescence are very close to the standard value of red, and the purity of red is very high. When used in architectural coatings, it has the properties of delayed luminescence, brightening brightness, being green, environmentally friendly and energy-saving.

[0008] A method for preparing a building luminous paint comprises the following steps: (A) Epoxy resin E-44 is heated to 35-40°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The luminescent powder is SrNb2O6:Eu 3+ , prepared by the following steps (1) Preparation of three-dimensional porous PS conductive materials; (2) Hydrophilic treatment of PS conductive materials: (3) preparing electrolyte; (4) Electrodeposition under negative pressure conditions; (5) Post-processing.

[0009] The electrolyte consists of strontium nitrate, niobium nitrate and europium nitrate, sodium citrate and citric acid, and deionized water.

[0010] The electrodeposition parameters under the negative pressure conditions are: vacuum degree of 0.4-0.5 MPa, constant potential deposition, temperature of 60-70° C., deposition voltage of -1.2~-1.7 V, and time of 1-2 h.

[0011] The preparation process of step (1) comprises the following steps: taking 7 mL of styrene and 1.6 mL of divinylbenzene and placing them in a three-necked flask, then adding 0.063 g of AIBN and 0.55 g of Span80, stirring the mixture evenly with a stirring rod, and then slowly dripping 34 mL of deionized water into the three-necked flask using a gravity infusion method, the dripping time being 60-62 min, and after the deionized water is injected, continuing to stir for 50 min, pouring the mixture into a test tube or a sheet disk mold, placing the mixture in a 60° C. drying furnace to react for 28 h, removing the reacted polymer from the mold, continuing to react at 60° C. for 30 h, taking the mixture out and cooling it naturally to obtain a PS template; placing the obtained PS template in a nitrogen atmosphere tubular furnace, heating the temperature to 650° C. at a heating rate of 1-2° C. / min, and calcining the mixture for 2-3 h.

[0012] The hydrophilic treatment of the PS conductive material comprises the following steps: immersing the PS conductive material prepared in step (1) in a newly prepared 0.01-0.015M strontium hydroxide aqueous solution, and evacuating the material with a vacuum pump to a vacuum degree of 0.01-0.1 MPa, so that the strontium hydroxide is absorbed into the pores of the PS conductive material, and then drying and heat treating the material at 60° C. for 30 minutes.

[0013] The electrolyte preparation process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them evenly to prepare the electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2mM: (1.4-1.6)mM: (1.0-1.2)mM.

[0014] During electrodeposition under negative pressure conditions, the PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode.

[0015] The conductive material is in the form of a sheet or a rod.

[0016] The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800° C. at a heating rate of 1-2° C. / min, and calcine it for 30-50 minutes. The muffle furnace is in an air atmosphere.

[0017] The post-treatment step includes heat treatment and grinding. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh.

[0018] A luminous building material coating composition comprises the following raw materials in parts by weight: component A: component B = 5-10:1; Component A: 20-30 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 15-20 parts of polyurethane resin; 15-20 parts of luminescent powder; 10-15 parts of titanium dioxide; 8-9 parts of corundum; 6-7 parts of talc; 5-8 parts of aluminum oxide; 1-2 parts of hydroxycarboxymethyl cellulose; 15-20 parts of acetone. Component B: 1-2 parts of triethanolamine; 0.5-0.8 parts of ethylenediamine.

[0019] Regarding the present invention, a porous three-dimensional PS template is first selected. The main reason is that the preparation of the corresponding PS template in the existing technology is mature, and macropores and mesopores can be obtained. The high specific surface area gives the subsequent hydroxide extremely high deposition sites, but the PS template itself is not conductive. In order to give the PS template conductivity under the premise of maintaining the stability of the PS pores, the PS needs to be carbonized and conductively treated, mainly by treating the PS template in a high-temperature inert atmosphere, which can not only achieve conductivity through heat treatment of carbonized polystyrene, but also maintain the overall macropores and mesopores of the PS template, as well as macroscopic flakes or rods. The PS template that has been conductively treated has poor hydrophilicity in this application and needs to be hydrophilically treated to prepare SrNb2O6:Eu subsequently. 3+ The strontium hydroxide in the electrolyte can effectively improve the hydrophilicity of PS and assist the negative pressure to increase the loading amount. Then, the hydroxide is deposited electrochemically. The deposition principle is that the cathode working electrode consumes hydrogen ions to release hydrogen, locally produces OH-, and uses a buffer to maintain the stability of the electrolyte. The locally produced superalkaline state forms hydroxide precipitation with Sr, Nb, Eu ions in the porous channels of the cathode. Then, the hydroxide of PS- (Sr, Nb, Eu) is heat-treated. The purpose of heat treatment is twofold. One is to form luminescent SrNb2O6:Eu through high-temperature heat treatment. 3+ Materials, secondly, by burning carbon at high temperature under air conditions, gasifying it and removing the carbonized PS template, only high-purity SrNb2O6:Eu is obtained 3+ Materials, the SrNb2O6:Eu 3+ The material can maintain a flake or rod shape, but the mechanical effect is poor and cannot be used directly. It needs to be crushed and graded to obtain the required powder particle size.

[0020] Beneficial technical effect: The present invention uses the electroplating template method to create a local superalkaline state and finally obtain SrNb2O6:Eu 3+ The material emits red light under ultraviolet light excitation, which is close to the standard value of red luminescent powder of the National Television Standards Committee (NTSC) (0.670, 0.330). The color purity can be calculated by the equation to be 99%. The luminescent paint prepared in this way was subjected to physical and chemical tests. The surface of the paint was smooth, and it can be judged that the paint flow has good parallelism, the paint film is stable, the initial brightness is high, the afterglow time is long, and the luminescence stability is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Attached Figure 1 CIE chromaticity diagram corresponding to the luminescent powder prepared in Example 2. DETAILED DESCRIPTION Example 1

[0022] A method for preparing a building luminous paint comprises the following steps: (A) Epoxy resin E-44 is heated to 35°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, and after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The architectural luminous paint includes the following raw materials in mass parts: the following raw materials in mass parts: component A: component B = 5:1; Component A: 20 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 15 parts of polyurethane resin; 15 parts of luminescent powder; 10 parts of titanium dioxide; 8 parts of corundum; 6 parts of talc; 5 parts of aluminum oxide; 1 part of hydroxycarboxymethyl cellulose; 15 parts of acetone. Component B: 1 part of triethanolamine; 0.5 parts of ethylenediamine.

[0023] SrNb2O6:Eu 3+ The luminescent powder is prepared by the following steps including the following steps.

[0024] (1) Preparation of three-dimensional porous PS conductive material: 7 mL of styrene and 1.6 mL of divinylbenzene were placed in a three-necked flask, and then 0.063 g of AIBN and 0.55 g of Span80 were added. After the mixture was stirred evenly with a stirring rod, 34 mL of deionized water was slowly dripped into the three-necked flask using a gravity infusion method for 60 min. After the deionized water was injected, stirring was continued for 50 min. The mixture was poured into a test tube or a sheet disk mold and placed in a 60 °C drying oven to react for 28 h. The reacted polymer was removed from the mold and continued to react at 60 °C for 30 h. The template was taken out and cooled naturally to obtain a PS template. The obtained PS template was placed in a nitrogen atmosphere tubular furnace and heated to 650 °C at a heating rate of 1 °C / min and calcined for 2 h.

[0025] (2) Hydrophilic treatment of PS conductive material: The steps for hydrophilic treatment of PS conductive material are as follows: soak the PS conductive material prepared in step (1) in a freshly prepared 0.01M strontium hydroxide aqueous solution, and use a vacuum water pump to evacuate the material to a vacuum degree of 0.01MPa, so that strontium hydroxide is absorbed into the pores of the PS conductive material, and then dry and heat-treat the material at 60°C for 30 minutes.

[0026] (3) preparing an electrolyte, the process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them uniformly to prepare an electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2 mM: (1.4) mM: (1.0) mM.

[0027] (4) Electrodeposition under negative pressure: The PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode to carry out electrodeposition. The electrodeposition parameters are: vacuum degree of 0.4 MPa, constant potential deposition, temperature of 60°C, deposition voltage of -1.2~V, and time of 1 h.

[0028] (5) Post-treatment: The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800°C at a heating rate of 1°C / min, and calcine it for 30 minutes. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh. Example 2

[0029] A method for preparing a building luminous paint comprises the following steps: (A) Epoxy resin E-44 is heated to 37.5°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, and after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The architectural luminous paint includes the following raw materials in mass parts: the following raw materials in mass parts: component A: component B = 7.5:1; Component A: 25 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 17.5 parts of polyurethane resin; 17.5 parts of luminescent powder; 12.5 parts of titanium dioxide; 8.5 parts of corundum; 6.5 parts of talc; 6.5 parts of aluminum oxide; 1.5 parts of hydroxycarboxymethyl cellulose; 17.5 parts of acetone. Component B: 1.5 parts of triethanolamine; 0.65 parts of ethylenediamine.

[0030] SrNb2O6:Eu 3+ The luminescent powder is prepared by the following steps including the following steps.

[0031] (1) Preparation of three-dimensional porous PS conductive material: 7 mL of styrene and 1.6 mL of divinylbenzene were placed in a three-necked flask, and then 0.063 g of AIBN and 0.55 g of Span80 were added. After the mixture was stirred evenly with a stirring rod, 34 mL of deionized water was slowly dripped into the three-necked flask using a gravity infusion method for 61 min. After the deionized water was injected, stirring was continued for 50 min. The mixture was poured into a test tube or a sheet disk mold and placed in a 60°C drying oven for reaction for 28 h. The reacted polymer was removed from the mold and continued to react at 60°C for 30 h. The template was taken out and cooled naturally to obtain a PS template. The obtained PS template was placed in a nitrogen atmosphere tubular furnace and heated to 650°C at a heating rate of 1.5°C / min and calcined for 2.5 h.

[0032] (2) Hydrophilic treatment of PS conductive material: The steps for hydrophilic treatment of PS conductive material are as follows: soak the PS conductive material prepared in step (1) in a freshly prepared 0.0125M strontium hydroxide aqueous solution, and use a vacuum water pump to evacuate the material to a vacuum degree of 0.05 MPa, so that strontium hydroxide is absorbed into the pores of the PS conductive material, and then dry and heat-treat the material at 60°C for 30 minutes.

[0033] (3) preparing an electrolyte, the process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them to obtain an electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2 mM: (1.5) mM: (1.1) mM.

[0034] (4) Electrodeposition under negative pressure: The PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode to carry out electrodeposition. The electrodeposition parameters are: vacuum degree of 0.45 MPa, constant potential deposition, temperature of 65°C, deposition voltage of -1.5 V, and time of 1.5 h.

[0035] (5) Post-treatment: The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800°C at a heating rate of 1.5°C / min, and calcine it for 40 minutes. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh. Example 3

[0036] A method for preparing a building luminous paint comprises the following steps: (A) Epoxy resin E-44 is heated to 40°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, and after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The architectural luminous paint includes the following raw materials in mass parts: the following raw materials in mass parts: component A: component B = 10:1; Component A: 30 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 20 parts of polyurethane resin; 20 parts of luminescent powder; 15 parts of titanium dioxide; 9 parts of corundum; 7 parts of talc; 8 parts of aluminum oxide; 2 parts of hydroxycarboxymethyl cellulose; 20 parts of acetone. Component B: 2 parts of triethanolamine; 0.8 parts of ethylenediamine.

[0037] SrNb2O6:Eu 3+ The luminescent powder is prepared by the following steps including the following steps.

[0038] (1) Preparation of three-dimensional porous PS conductive material: 7 mL of styrene and 1.6 mL of divinylbenzene were placed in a three-necked flask, and then 0.063 g of AIBN and 0.55 g of Span80 were added. After the mixture was stirred evenly with a stirring rod, 34 mL of deionized water was slowly dripped into the three-necked flask using a gravity infusion method for 62 min. After the deionized water was injected, stirring was continued for 50 min. The mixture was poured into a test tube or a sheet disk mold and placed in a 60°C drying oven for reaction for 28 h. The reacted polymer was removed from the mold and continued to react at 60°C for 30 h. The template was taken out and cooled naturally to obtain a PS template. The obtained PS template was placed in a nitrogen atmosphere tubular furnace and heated to 650°C at a heating rate of 2°C / min and calcined for 3 h.

[0039] (2) Hydrophilic treatment of PS conductive material: The steps for hydrophilic treatment of PS conductive material are as follows: soak the PS conductive material prepared in step (1) in a freshly prepared 0.015M strontium hydroxide aqueous solution, and use a vacuum water pump to evacuate the material to a vacuum degree of 0.1 MPa, so that strontium hydroxide is absorbed into the pores of the PS conductive material, and then dry and heat-treat the material at 60°C for 30 minutes.

[0040] (3) preparing an electrolyte, the process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH value of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them uniformly to prepare an electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2 mM: (1.6) mM: (1.2) mM.

[0041] (4) Electrodeposition under negative pressure: Electrodeposition was carried out using the PS conductive material prepared in step (2) as the working electrode, the platinum electrode as the counter electrode, and the silver / silver chloride electrode as the working electrode. The electrodeposition parameters were: vacuum degree of 0.5 MPa, constant potential deposition, temperature of 70°C, deposition voltage of -1.7 V, and time of 2 h.

[0042] (5) Post-treatment: The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800°C at a heating rate of 2°C / min, and calcine it for 50 minutes. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh.

[0043] Comparative Example 1, a method for preparing a building luminous coating, comprising the following steps: (A) Epoxy resin E-44 is heated to 37.5°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, and after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The architectural luminous paint includes the following raw materials in mass parts: the following raw materials in mass parts: component A: component B = 7.5:1; Component A: 25 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 17.5 parts of polyurethane resin; 17.5 parts of luminescent powder; 12.5 parts of titanium dioxide; 8.5 parts of corundum; 6.5 parts of talc; 6.5 parts of aluminum oxide; 1.5 parts of hydroxycarboxymethyl cellulose; 17.5 parts of acetone. Component B: 1.5 parts of triethanolamine; 0.65 parts of ethylenediamine.

[0044] SrNb2O6:Eu 3+ The luminescent powder is prepared by the following steps including the following steps.

[0045] (1) Preparation of three-dimensional porous PS conductive material: 7 mL of styrene and 1.6 mL of divinylbenzene were placed in a three-necked flask, and then 0.063 g of AIBN and 0.55 g of Span80 were added. After the mixture was stirred evenly with a stirring rod, 34 mL of deionized water was slowly dripped into the three-necked flask using a gravity infusion method for 61 min. After the deionized water was injected, stirring was continued for 50 min. The mixture was poured into a test tube or a sheet disk mold and placed in a 60°C drying oven for reaction for 28 h. The reacted polymer was removed from the mold and continued to react at 60°C for 30 h. The template was taken out and cooled naturally to obtain a PS template. The obtained PS template was placed in a nitrogen atmosphere tubular furnace and heated to 650°C at a heating rate of 1.5°C / min and calcined for 2.5 h.

[0046] (2) Hydrophilic treatment of PS conductive material: The steps for hydrophilic treatment of PS conductive material are as follows: soak the PS conductive material prepared in step (1) in a freshly prepared 0.0125M strontium hydroxide aqueous solution, and use a vacuum water pump to evacuate the material to a vacuum degree of 0.05 MPa, so that strontium hydroxide is absorbed into the pores of the PS conductive material, and then dry and heat-treat the material at 60°C for 30 minutes.

[0047] (3) preparing an electrolyte, the process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH of the buffer system is 6.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them uniformly to prepare an electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2 mM: (1.5) mM: (1.1) mM.

[0048] (4) Electrodeposition under negative pressure: The PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode to carry out electrodeposition. The electrodeposition parameters are: vacuum degree of 0.45 MPa, constant potential deposition, temperature of 65°C, deposition voltage of -1.5 V, and time of 1.5 h.

[0049] (5) Post-treatment: The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800°C at a heating rate of 1.5°C / min, and calcine it for 40 minutes. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh.

[0050] Comparative Example 2, a method for preparing a building luminous coating, comprising the following steps: (A) Epoxy resin E-44 is heated to 37.5°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, and after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) Titanium dioxide, talcum powder, aluminum oxide, corundum, and hydroxycarboxymethyl cellulose are dissolved in acetone and then ground at high speed. , mixed with the mixed resin liquid obtained in step (A), and stirred evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The architectural luminous paint includes the following raw materials in mass parts: the following raw materials in mass parts: component A: component B = 7.5:1; Component A: 25 parts of E-44 epoxy resin liquid containing 60% epoxy resin; 17.5 parts of polyurethane resin; 17.5 parts of luminescent powder; 12.5 parts of titanium dioxide; 8.5 parts of corundum; 6.5 parts of talc; 6.5 parts of aluminum oxide; 1.5 parts of hydroxycarboxymethyl cellulose; 17.5 parts of acetone. Component B: 1.5 parts of triethanolamine; 0.65 parts of ethylenediamine.

[0051] SrNb2O6:Eu 3+ The luminescent powder is prepared by the following steps including the following steps.

[0052] (1) Preparation of three-dimensional porous PS conductive material: 7 mL of styrene and 1.6 mL of divinylbenzene were placed in a three-necked flask, and then 0.063 g of AIBN and 0.55 g of Span80 were added. After the mixture was stirred evenly with a stirring rod, 34 mL of deionized water was slowly dripped into the three-necked flask using a gravity infusion method for 61 min. After the deionized water was injected, stirring was continued for 50 min. The mixture was poured into a test tube or a sheet disk mold and placed in a 60°C drying oven for reaction for 28 h. The reacted polymer was removed from the mold and continued to react at 60°C for 30 h. The template was taken out and cooled naturally to obtain a PS template. The obtained PS template was placed in a nitrogen atmosphere tubular furnace and heated to 650°C at a heating rate of 1.5°C / min and calcined for 2.5 h.

[0053] (2) preparing an electrolyte, the process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH value of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them uniformly to prepare an electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2 mM: (1.5) mM: (1.1) mM.

[0054] (3) Electrodeposition under negative pressure conditions: The PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode to carry out electrodeposition. The electrodeposition parameters are: vacuum degree of 0.45 MPa, constant potential deposition, temperature of 65°C, deposition voltage of -1.5 V, and time of 1.5 h.

[0055] (4) Post-treatment: The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800°C at a heating rate of 1.5°C / min, and calcine it for 40 minutes. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh.

[0056] See attached Figure 1 For Example 2, under ultraviolet excitation, SrNb2O6:Eu 3+ The CIE chromaticity coordinates of the luminescent powder are determined based on the photoluminescence spectrum. The photoluminescence color coordinates of Example 2 (0.644, 0.350) are close to the standard values ​​of the red luminescent powder of the National Television Standards Committee (NTSC) (0.670, 0.330), and the color purity can be calculated by the equation to be 99%. In comparison, the buffer system of Comparative Example 1 is different from that of Example 2, and the corresponding photoluminescence color coordinates (0.632, 0.356) and the color purity can be calculated by the equation to be 96%. Comparative Example 2 lacks a hydrophilic treatment process, and the corresponding photoluminescence color coordinates (0.619, 0.345) and the color purity can be calculated by the equation to be 91%, that is, the red purity of Example 2 is very high, which is the best result, showing the technical contribution of the pH value of the buffer system and the hydrophilic treatment process of the present invention to the luminescent powder. The coating prepared in Example 2 was subjected to physical and chemical tests. The coating surface was smooth, and it can be judged that the coating flow parallelism was good and the coating film was stable. The coating prepared in Example 2 was characterized. After irradiation with ultraviolet light, the initial brightness was approximately equal to 1433mcd / m 2 The afterglow time is greater than 2.8h. After repeated irradiation, there is no obvious change in the initial brightness and afterglow time, showing extremely high luminescence stability. After the coating is immersed in weak alkaline water with pH=7.2 for 48 hours, the initial brightness decreases by about 13%. The reason may be attributed to the hydrolysis of the luminescent material or the insufficient density of the coating. Compared with the technical effect corresponding to Comparative Example 1-2, it is not ideal.

[0057] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a building luminous coating, characterized in that The steps include: (A) Epoxy resin E-44 is heated to 35-40°C in cyclohexanone to dissolve into epoxy resin liquid containing 60% epoxy resin, luminescent powder is added to the epoxy resin liquid in proportion, after high-speed grinding, polyurethane is added in proportion to obtain a mixed resin liquid; (B) dissolving titanium dioxide, talc, aluminum oxide, corundum and hydroxycarboxymethyl cellulose in acetone, grinding at high speed, mixing with the mixed resin liquid obtained in step (A), and stirring evenly to obtain component A; (C) preparing component B by mixing triethanolamine and hexamethylenediamine; mixing component A and component B in proportion, stirring evenly and applying the mixture to the surface of the building material by brushing; The luminescent powder is SrNb2O6:Eu 3+ , prepared by the following steps (1) Preparation of three-dimensional porous PS conductive materials; (2) Hydrophilic treatment of PS conductive materials: (3) preparing electrolyte; (4) Electrodeposition under negative pressure conditions; (5) Post-processing: The electrolyte is composed of strontium nitrate, niobium nitrate and europium nitrate, sodium citrate and citric acid, and deionized water; The electrodeposition parameters under the negative pressure conditions are: vacuum degree of 0.4-0.5 MPa, constant potential deposition, temperature of 60-70° C., deposition voltage of -1.2~-1.7 V, and time of 1-2 h.

2. The method for preparing a building luminous paint according to claim 1, characterized in that The preparation process of step (1) comprises the following steps: taking 7 mL of styrene and 1.6 mL of divinylbenzene and placing them in a three-necked flask, then adding 0.063 g of AIBN and 0.55 g of Span80, stirring the mixture evenly with a stirring rod, and then slowly dripping 34 mL of deionized water into the three-necked flask using a gravity infusion method, the dripping time being 60-62 min, and after the deionized water is injected, continuing to stir for 50 min, pouring the mixture into a test tube or a sheet disk mold, placing the mixture in a 60° C. drying furnace to react for 28 h, removing the reacted polymer from the mold, continuing to react at 60° C. for 30 h, taking the mixture out and cooling it naturally to obtain a PS template; placing the obtained PS template in a nitrogen atmosphere tubular furnace, heating the temperature to 650° C. at a heating rate of 1-2° C. / min, and calcining the mixture for 2-3 h.

3. The method for preparing a building luminous paint according to claim 1, characterized in that The hydrophilic treatment of the PS conductive material comprises the following steps: immersing the PS conductive material prepared in step (1) in a newly prepared 0.01-0.015M strontium hydroxide aqueous solution, and evacuating the material with a vacuum pump to a vacuum degree of 0.01-0.1 MPa, so that the strontium hydroxide is absorbed into the pores of the PS conductive material, and then drying and heat treating the material at 60° C. for 30 minutes.

4. The method for preparing a building luminous paint according to claim 1, characterized in that The electrolyte preparation process is as follows: (a) preparing a sodium citrate and citric acid buffer solution system, wherein the pH of the buffer system is 4.2±0.1; (b) adding strontium nitrate, niobium nitrate and europium nitrate to the buffer solution system, and stirring them evenly to prepare the electrolyte; the ratio of strontium nitrate, niobium nitrate and europium nitrate in the electrolyte is 0.2mM: (1.4-1.6)mM: (1.0-1.2)mM.

5. The method for preparing a building luminous paint according to claim 1, characterized in that During electrodeposition under negative pressure conditions, the PS conductive material prepared in step (2) is used as the working electrode, the platinum electrode is used as the counter electrode, and the silver / silver chloride electrode is used as the working electrode.

6. The method for preparing a building luminous paint according to claim 1, characterized in that The conductive material is in the form of a sheet or a rod.

7. The method for preparing a building luminous paint according to claim 1, characterized in that The post-treatment step includes heat treatment and grinding. The heat treatment is to place the sample obtained in the preparation step (5) in a muffle furnace, heat it to 800° C. at a heating rate of 1-2° C. / min, and calcine it for 30-50 minutes. The muffle furnace is in an air atmosphere.

8. The method for preparing a building luminous paint according to claim 1, characterized in that The post-treatment step includes heat treatment and grinding. After grinding, the ground powder is classified according to the particle size using an air flow classifier, and the preferred particle size range is 100-500 mesh.

9. A coating component obtained by the preparation method according to any one of claims 1 to 8, characterized in that Including the following raw materials by mass: Component A: Component B = 5-10:1; Component A: 20-30 parts of E-44 epoxy resin liquid containing 60% epoxy resin; Polyurethane resin 15-20 parts; 15-20 parts of luminous powder; 10-15 parts of titanium dioxide; 8-9 parts of corundum; 6-7 parts of talcum powder; 5-8 parts of aluminum oxide; 1-2 parts of hydroxycarboxymethyl cellulose; 15-20 parts of acetone; Component B: 1-2 parts of triethanolamine; Ethylenediamine 0.5-0.8 parts.

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